Published Papers - HAYASHI Satoko

Extremely stable system of 1-haloselanyl-anthraquinones: Experimental and theoretical investigations

Naoki Ogawa, Nobuhiro Suzuki, Yoshifumi Katsura, Mao Minoura, Waro Nakanishi, Satoko Hayashi （Part： Corresponding author )

Dalton Transactions   53   10099 - 10112   2024.05  [Refereed]

Origin of 13C NMR chemical shifts elucidated based on molecular orbital theory: paramagnetic contributions from orbital-to-orbital transitions for the pre-α, α, β, α-X, β-X and ipso-X effects, along with effects from characteristic bonds and groups.

Waro Nakanishi, Satoko Hayashi, Keigo Matsuzaki （Part： Corresponding author )

RSC advances ( the Royal Society of Chemistry )  15 ( 3 ) 1924 - 1940   2025.01  [Refereed]

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13C NMR chemical shifts (δ(C)) were analysed via MO theory, together with the origin, using σ d(C), σ p(C) and σ t(C), where C4- was selected as the standard for the analysis since σ p(C: C4-) = 0 ppm. An excellent relationship was observed between σ d(C) and the charges on C for (C4+, C2+, C0, C2- and C4-) and (C4-, CH2 2-, CH3 - and CH4). However, such a relationship was not observed for the carbon species other than those above. The occupied-to-unoccupied orbital (ψ i →ψ a ) transitions were mainly employed for the analysis. The origin was explained by the pre-α, α, β, α-X, β-X and ipso-X effects. The pre-α effect of an approximately 20 ppm downfield shift is theoretically predicted, and the observed α and β effects of approximately 10-15 ppm downfield shifts are well reproduced by the calculations, as are the variations in the α-X, β-X and ipso-X effects. Large downfield shifts caused by the formation of ethene (∼120 ppm), ethyne (∼60 ppm) and benzene (∼126 ppm) from ethane and carbonyl (∼146 ppm) and carboxyl (∼110 ppm) groups from CH3OH are also reproduced well by the calculations. The analysis and illustration of σ p(C) through the ψ i →ψ a transitions enables us to visualize the effects and to understand the δ(C) values for the C atoms in the specific positions of the species. The occupied-to-occupied orbital (ψ i →ψ j ) transitions are also examined. The theoretical investigations reproduce the observed results of δ(C). The origin for δ(C) and the mechanism are visualized, which allows us to image the process in principle. The role of C in the specific position of a compound in question can be more easily understood, which will aid in the development of highly functional compounds based on NMR.

DOI

Origin of ¹⁷O NMR chemical shifts based on molecular orbital theory: paramagnetic terms of the pre-α, α and β effects from orbital-to-orbital transitions, along with the effects from vinyl, carbonyl and carboxyl groups

Keigo Matsuzaki, Satoko Hayashi, Waro Nakanishi （Part： Corresponding author )

RSC Advances ( Royal Society of Chemistry (RSC) )  14 ( 20 ) 14340 - 14356   2024.04  [Refereed]

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The plain rules founded in theory, other than the empirical rules, were established for the origin of δ(O) to understand the mechanisms to arise ¹⁷O NMR chemical shifts, based on the MO theory, where the pre-α, α and β effects were employed for the purpose, which were analyzed mainly by σ^p(O).

DOI

Intrinsic dynamic and static natures of ^APn--X⁺--^BPn σ(3c–4e) type interactions (^APn = ^BPn = N, P, As and Sb; X = H, F, Cl, Br and I) in bicyclo[3.3.3] and bicyclo[4.4.4] systems and their behaviour, elucidated with QTAIM dual functional analysis

Taro Nishide, Waro Nakanishi, Satoko Hayashi （Part： Corresponding author )

RSC Advances ( Royal Society of Chemistry (RSC) )  14 ( 8 ) 5675 - 5689   2024.01  [Refereed]

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Natures of the symmetric and nonsymmetric Pn⋯X⁺⋯Pn σ(3c–4e) type interactions (Pn = N, P, As and Sb; X = H, F, Cl, Br and I) in bicyclo[3.3.3] and [4.4.4] systems are elucidated, after clarifying the stability, where X⁺ incorporated in the cage.

DOI

Dynamic and Static Nature of XH-∗-π and YX-∗-π (X = F, Cl, Br, and I; Y = X and F) in the Distorted π-System of Corannulene Elucidated with QTAIM Dual Functional Analysis

Satoko Hayashi, Takahiro Kato, Yuji Sugibayashi, Waro Nakanishi （Part： Lead author,　Corresponding author )

Molecules ( MDPI AG )  28 ( 10 ) 4219 - 4219   2023.05  [Refereed]

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The dynamic and static nature of the XH-∗-π and YX-∗-π (X = F, Cl, Br, and I; Y = X and F) interactions in the distorted π-system of corannulene (π(C20H10)) is elucidated with a QTAIM dual functional analysis (QTAIM-DFA), where asterisks emphasize the presence of bond critical points (BCPs) on the interactions. The static and dynamic nature originates from the data of the fully optimized and perturbed structures, respectively, in QTAIM-DFA. On the convex side, H in F–H-∗-π(C20H10) and each X in Y–X-∗-π(C20H10) join to C of the central five-membered ring in π(C20H10) through a bond path (BP), while each H in X–H-∗-π(C20H10) does so to the midpoint of C=C in the central five-membered ring for X = Cl, Br, or I. On the concave side, each X in F–X-∗-π(C20H10) also joins to C of the central five-membered ring with a BP for X = H, Cl, Br, and I; however, the interactions in other adducts are more complex than those on the convex side. Both H and X in X–H-∗-π(C20H10) (X = Cl and Br) and both Fs in F–F-∗-π(C20H10) connect to the three C atoms in each central five-membered ring (with three BPs). Two, three, and five BPs were detected for the Cl–Cl, I–H, Br–Br, and I–I adducts, where some BPs do not stay on the central five-membered ring in π(C20H10). The interactions are predicted to have a vdW to CT-MC nature. The interactions on the concave side seem weaker than those on the convex side for X–H-∗-π(C20H10), whereas the inverse trend is observed for Y–X-∗-π(C20H10) as a whole. The nature of the interactions in the π(C20H10) adducts of the convex and concave sides is examined in more detail, employing the adducts with X–H and F–X placed on their molecular axis together with the π(C24H12) and π(C6H6) adducts.

DOI

Synthesis, structures and reactions of acylsulfenyl iodides with theoretical investigations

Shinzi Kato, Masahiro Kimura, Yukio Komatsu, Kenji Miyagawa, Masaru Ishida, Masahiro Ebihara, Osamu Niyomura, Waro Nakanishi, Satoko Hayashi （Part： Corresponding author )

RSC Advances ( Royal Society of Chemistry (RSC) )  13 ( 18 ) 12035 - 12049   2023.04  [Refereed]

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A series of acylsulfenyl iodides (RCOSI) were synthesized by the reactions of carbothioic acid group 11–16 element derivatives with iodine or N-iodosuccinimides in moderate to good yields.

DOI

Inverse Versus Normal Behavior of Interactions, Elucidated Based on the Dynamic Nature with QTAIM Dual-Functional Analysis

Waro Nakanishi, Satoko Hayashi, Ryosuke Imanaka, Taro Nishide, Eiichiro Tanaka, Hikaru Matsuoka （Part： Last author,　Corresponding author )

International Journal of Molecular Sciences ( MDPI AG )  24 ( 3 ) 2798 - 2798   2023.02  [Refereed]  [Invited]

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In QTAIM dual-functional analysis, Hb(rc) is plotted versus Hb(rc) − Vb(rc)/2 for the interactions, where Hb(rc) and Vb(rc) are the total electron energy densities and potential energy densities, respectively, at the bond critical points (BCPs) on the interactions in question. The plots are analyzed by the polar (R, θ) coordinate representation for the data from the fully optimized structures, while those from the perturbed structures around the fully optimized structures are analyzed by (θp, κp). θp corresponds to the tangent line of the plot, and κp is the curvature; θ and θp are measured from the y-axis and y-direction, respectively. The normal and inverse behavior of interactions is proposed for the cases of θp > θ and θp < θ, respectively. The origin and the mechanism for the behavior are elucidated. Interactions with θp < θ are typically found, although seldom for [F–I-∗-F]−, [MeS-∗-TeMe]2+, [HS-∗-TeH]2+ and CF3SO2N-∗-IMe, where the asterisks emphasize the existence of BCPs in the interactions and where [Cl–Cl-∗-Cl]− and CF3SO2N-∗-BrMe were employed as the reference of θp > θ. The inverse behavior of the interactions is demonstrated to arise when Hb(rc) − Vb(rc)/2 and when the corresponding Gb(rc), the kinetic energy densities at BCPs, does not show normal behavior.

DOI

Proposal of pseudo-intrinsic dynamic nature of interactions: simple methods to generate the perturbed structures and to analyze for the prediction of the nature of high reliability, with the applications

Satoko Hayashi, Taro Nishide, Hikaru Matsuoka, Ryosuke Imanaka, Waro Nakanishi （Part： Lead author,　Last author,　Corresponding author )

Arkivoc ( ARKAT USA, Inc. )  2023 ( 5 ) 93 - 116   2022.12  [Refereed]  [Invited]

DOI

Intrinsic Dynamic and Static Nature of π---π Interactions in Fused Benzene-Type Helicenes and Dimers, Elucidated with QTAIM Dual Functional Analysis

Taro Nishide, Satoko Hayashi （Part： Corresponding author )

Nanomaterials ( MDPI )  12 ( 3 ) 321-1 - 321-19   2022.02  [Refereed]  [Invited]

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The intrinsic dynamic and static nature of the pi center dot center dot center dot pi interactions between the phenyl groups in proximity of helicenes 3-12 are elucidated with the quantum theory of atoms-in-molecules dual functional analysis (QTAIM-DFA). The pi center dot center dot center dot pi interactions appear in C-*-C, H-*-H, and C-*-H, with the asterisks indicating the existence of bond critical points (BCPs) on the interactions. The interactions of 3-12 are all predicted to have a p-CS/vdW nature (vdW nature of the pure closed-shell interaction), except for C-2(bay)-*-C-7(bay) of 10, which has a p-CS/t-HBnc nature (typical-HBs with no covalency). (See the text for definition of the numbers of C and the bay and cape areas). The natures of the interactions are similarly elucidated between the components of helicene dimers 6:6 and 7:7 with QTAIM-DFA, which have a p-CS/vdW nature. The characteristic electronic structures of helicenes are clarified through the natures predicted with QTAIM-DFA. Some bond paths (BPs) in helicenes appeared or disappeared, depending on the calculation methods. The static nature of C-cape-*-C-cape is very similar to that of C-bay-*-C-bay in 9-12, whereas the dynamic nature of C-cape-*-C-cape appears to be very different from that of C-bay-*-C-bay. The results will be a guide to design the helicene-containing materials of high functionality.

DOI

Intrinsic Dynamic and Static Nature of Halogen Bonding in Neutral Polybromine Clusters, with the Structural Feature Elucidated by QTAIM Dual-Functional Analysis and MO Calculations

Satoko Hayashi, Taro Nishide, Eiichiro Tanaka, Waro Nakanishi （Part： Lead author,　Corresponding author )

Molecules ( MDPI AG )  26 ( 10 ) 2936 - 2936   2021.05  [Refereed]

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The intrinsic dynamic and static nature of noncovalent Br-∗-Br interactions in neutral polybromine clusters is elucidated for Br4–Br12, applying QTAIM dual-functional analysis (QTAIM-DFA). The asterisk (∗) emphasizes the existence of the bond critical point (BCP) on the interaction in question. Data from the fully optimized structures correspond to the static nature of the interactions. The intrinsic dynamic nature originates from those of the perturbed structures generated using the coordinates derived from the compliance constants for the interactions and the fully optimized structures. The noncovalent Br-∗-Br interactions in the L-shaped clusters of the Cs symmetry are predicted to have the typical hydrogen bond nature without covalency, although the first ones in the sequences have the vdW nature. The L-shaped clusters are stabilized by the n(Br)→σ*(Br–Br) interactions. The compliance constants for the corresponding noncovalent interactions are strongly correlated to the E(2) values based on NBO. Indeed, the MO energies seem not to contribute to stabilizing Br4 (C2h) and Br4 (D2d), but the core potentials stabilize them, relative to the case of 2Br2; this is possibly due to the reduced nuclear–electron distances, on average, for the dimers.

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Linear Multiselenium Interactions in Dicationic Oligomers of 1,5‐(Diselena)canes: Behavior of σ( mc^c‐ne^e) (6≤ mc ≤16) Elucidated with QTAIM Dual Functional Analysis

Satoko Hayashi, Taro Nishide, Kengo Nagata, Waro Nakanishi （Part： Lead author,　Corresponding author )

ChemistryOpen ( Wiley )  10   656 - 665   2021.05  [Refereed]

DOI

Synthesis and Characterization of Monomeric Hexacoordinated Chalcogenonium Salts Bearing 2-(2-Pyridyl)phenyl Ligands

Soichi Sato, Akihisa Ooizumi, Masato Sakabe, Koh Funahashi, Wataru Fujita, Satoko Hayashi, Waro Nakanishi （Part： Corresponding author )

Bulletin of the Chemical Society of Japan ( The Chemical Society of Japan )  94 ( 4 ) 1192 - 1200   2021.04  [Refereed]

DOI

Dynamic and Static Nature of Br4 σ(4c–6e) and Se2Br5 σ(7c–10e) in the Selenanthrene System and Related Species Elucidated by QTAIM Dual Functional Analysis with QC Calculations

Satoko Hayashi, Taro Nishide, Waro Nakanishi （Part： Lead author )

Bioinorganic Chemistry and Applications ( Hindawi Limited )  2020   2901439-1 - 14   2020.07  [Refereed]

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The nature of Br₄<italic>σ</italic>(4c–6e) of the ^BBr-∗-^ABr-∗-^ABr-∗-^BBr form is elucidated for SeC₁₂H₈(Br)Se<bold>Br---Br-Br---Br</bold>Se(Br)C₁₂H₈Se, the selenanthrene system, and the models with QTAIM dual functional analysis (QTAIM-DFA). Asterisks (∗) are employed to emphasize the existence of bond critical points on the interactions in question. Data from the fully optimized structure correspond to the static nature of interactions. In our treatment, data from the perturbed structures, around the fully optimized structure, are employed for the analysis, in addition to those from the fully optimized one, which represent the dynamic nature of interactions. The ^ABr-∗-^ABr and ^ABr-∗-^BBr interactions are predicted to have the CT-TBP (trigonal bipyramidal adduct formation through charge transfer) nature and the typical hydrogen bond nature, respectively. The nature of Se₂Br₅<italic>σ</italic>(7c–10e) is also clarified typically, employing an anionic model of [<bold>Br-Se</bold>(C₄H₄Se)<bold>-Br---Br---Br-Se</bold>(C₄H₄Se)<bold>-Br</bold>]⁻, the 1,4-diselenin system, rather than (BrSeC₁₂H₈)<bold>Br---Se---Br</bold>-<bold>Br---Br-Se</bold>(C₁₂H₈Se)<bold>-Br</bold>, the selenanthrene system.

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Intrinsic dynamic and static nature of each HB in the multi-HBs between nucleobase pairs and its behavior, elucidated with QTAIM dual functional analysis and QC calculations

Waro Nakanishi, Satoko Hayashi, Taro Nishide （Part： Corresponding author )

RSC Advances ( Royal Society of Chemistry (RSC) )  10 ( 41 ) 24730 - 24742   2020.06  [Refereed]

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<p>Each HB in nucleobase pairs (Nu–Nu′) has the nature close to that of a molecular complex, for example. Energies for the formation of Nu–Nu′ are linearly correlated with the summarized values of the compliance constant of each HB in Nu–Nu′.</p>

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The nature of G⋯E–Y σ(3c–4e) in o-MenGCH2C6H4EY (MenG = Me2N and MeE; E = O, S, Se and Te; Y = F, Cl, Br, EMe and Me) with contributions from CT and compliance constants in noncovalent G⋯E interactions

Satoko Hayashi, Taro Nishide, Waro Nakanishi, Luca Sancineto, Claudio Santi （Part： Lead author )

RSC Advances ( Royal Society of Chemistry (RSC) )  9 ( 67 ) 39435 - 39446   2019.11  [Refereed]

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<p>The nature of E⋯E′ in 1-RECH₂-2-R′E′C₆H₄ (E/E′ = O, S, Se and Te) is clarified with QTAIM approach and NBO analysis, after structural determinations.</p>

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Dynamic and static nature of activated interactions in transition states as elucidated by quantum theory of atoms-in-molecules dual functional analysis: A case of ligand exchange at the N of sulfonylimino-λ3-bromanes

Waro Nakanishi, Satoko Hayashi, Taro Nishide, Shota Otsuki

Int. J. Quantum Chem.   2019   e26073-1 - e26073-14   2019.11  [Refereed]

Nature of the E⋯E′ interactions (E, E′ = O, S, Se, and Te) at naphthalene 1,8-positions with fine details of the structures: experimental and theoretical investigations

Satoko Hayashi, Manabu Uegaito, Taro Nishide, Eiichiro Tanaka, Waro Nakanishi, Takahiro Sasamori, Norihiro Tokitoh, Mao Minoura （Part： Lead author )

New Journal of Chemistry ( Royal Society of Chemistry (RSC) )  43 ( 36 ) 14224 - 14237   2019.08  [Refereed]

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<p>The nature of E⋯E′ in 1-RE–8-R′E′C₁₀H₆ (E/E′ = O, S, Se and Te) is clarified with the QTAIM approach and NBO analysis, after structural determinations.</p>

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Effects from Basis Sets and Levels of Calculations on the Nature of Interactions Predicted by QTAIM Dual Functional Analysis with QTAIM Functions

Satoko Hayashi, Taro Nishide, Kazuki Ueda, Koki Hayama, Waro Nakanishi （Part： Lead author )

ChemistrySelect ( Wiley )  4 ( 20 ) 6198 - 6208   2019.05  [Refereed]

DOI

Nature of intramolecular O–H⋯π interactions as elucidated by QTAIM dual functional analysis with QC calculations

Satoko Hayashi, Taro Nishide, Waro Nakanishi （Part： Lead author )

RSC Advances ( Royal Society of Chemistry (RSC) )  9 ( 27 ) 15521 - 15530   2019.05  [Refereed]

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<p>Intramolecular OH–*–C(π), O–*–C(π) and O–*–H(π) interactions are detected as having a vdW nature, which is typical of an HB with no covalency.</p>

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Behavior of Multi-HBs in Acetic Acid Dimer and Related Species: QTAIM Dual Functional Analysis Employing Perturbed Structures Generated Using Coordinates from Compliance Force Constants

Satoko Hayashi, Taro Nishide, Waro Nakanishi （Part： Lead author )

Bulletin of the Chemical Society of Japan ( The Chemical Society of Japan )  92 ( 1 ) 87 - 96   2019.01  [Refereed]

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Behavior of I4 σ(4c-6e) in tellurolane system and related species, elucidated by QTAIM dual functional analysis with QC calculations

Satoko Hayashi, Taro Nishide, Waro Nakanishi （Part： Lead author )

Heteroatom Chemistry ( Wiley )  29 ( 5-6 ) e21462 - e21462   2018.12  [Refereed]

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Intrinsic Dynamic Nature of Neutral Hydrogen Bonds Elucidated with QTAIM Dual Functional Analysis: Role of the Compliance Force Constants and QTAIM-DFA Parameters in Stability

Taro Nishide, Satoko Hayashi, Waro Nakanishi

ChemistryOpen ( Wiley )  7 ( 8 ) 565 - 575   2018.08  [Refereed]

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Perturbed structures generated using coordinates derived from compliance constants in internal vibrations for QTAIM dual functional analysis: Intrinsic dynamic nature of interactions

Waro Nakanishi, Satoko Hayashi

International Journal of Quantum Chemistry ( Wiley )  118 ( 11 ) e25590 - e25590   2018.06  [Refereed]

DOI

Behaviour of the XH-*-π and YX-*-π interactions (X, Y = F, Cl, Br and I) in the coronene π-system, as elucidated by QTAIM dual functional analysis with QC calculations

Satoko Hayashi, Yuji Sugibayashi, Waro Nakanishi （Part： Lead author )

RSC Advances ( Royal Society of Chemistry (RSC) )  8 ( 29 ) 16349 - 16361   2018.04  [Refereed]

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<p>The XH-*-π(C₂₄H₁₂) interactions appear on the outside ring of C₂₄H₁₂, while YX-*-π(C₂₄H₁₂) do both on the inside and outside rings.</p>

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High-resolution X-ray diffraction determination of the electron density of 1-(8-PhSC10H6)SS(C10H6SPh-8′)-1′ with the QTAIM approach: evidence for S4 σ(4c–6e) at the naphthalene peri-positions

Yutaka Tsubomoto, Satoko Hayashi, Waro Nakanishi, Lucy K. Mapp, Simon J. Coles

RSC Advances ( Royal Society of Chemistry (RSC) )  8 ( 18 ) 9651 - 9660   2018.02  [Refereed]

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<p>The nature of S₄ σ(4c–6e) at the 1,8-positions of naphthalene is elucidated <italic>via</italic> a high-resolution X-ray method with the QTAIM approach.</p>

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Behavior of the E–E’ Bonds (E, E’ = S and Se) in Glutathione Disulfide and Derivatives Elucidated by Quantum Chemical Calculations with the Quantum Theory of Atoms-in-Molecules Approach

Satoko Hayashi, Yutaka Tsubomoto, Waro Nakanishi （Part： Lead author )

Molecules ( MDPI AG )  23 ( 2 ) 443 - 443   2018.02  [Refereed]

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Relativistic Effect on 1 J (M,C) in Me4 M, Me3 M− , Ph4 M, and Ph3 M− (M=Pb, Sn, Ge, Si, and/or C): Role of s-Type Lone Pair Orbitals in the Distinct Effect for the Anionic Species

Satoko Hayashi, Taro Nishide, Waro Nakanishi, Masaichi Saito （Part： Lead author )

ChemPhysChem ( Wiley )  18 ( 18 ) 2466 - 2474   2017.09  [Refereed]

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Behavior of interactions between hydrogen chalcogenides and an anthracene π-system elucidated by QTAIM dual functional analysis with QC calculations

Satoko Hayashi, Yuji Sugibayashi, Waro Nakanishi （Part： Lead author )

RSC Advances ( Royal Society of Chemistry (RSC) )  7 ( 51 ) 31858 - 31865   2017.05  [Refereed]

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<p>The nature of the interactions between chalcogenides and the anthracene p-system, EH₂-*-p(C₁₄H₁₀), is predicted to be close to that of EH₂-*-p(C₁₀H₈), although the partial structures around the central rings can be found in EH₂-*-p(C₆H₆).</p>

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Nature of E2X2 σ(4c-6e) of the X---E-E---X type at naphthalene 1,8-positions and model, elucidated by X-ray crystallographic analysis and QC calculations with the QTAIM approach

Yutaka Tsubomoto, Satoko Hayashi, Waro Nakanishi, Takahiro Sasamori, Norihiro Tokitoh

Acta Crystallographica Section B: Structural Science, Crystal Engineering and Materials ( International Union of Crystallography )  73 ( 2 ) 265 - 275   2017.04  [Refereed]  [Invited]

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The nature of E2X2 σ(4c-6e) of the X-∗-E-∗-E-∗-X type is elucidated for 1-(8-XC10H6)E-E(C10H6X-8')-1' [(1) E, X = S, Cl
(2) S, Br
(3) Se, Cl
(4) Se, Br] after structural determination of (1), (3) and (4), together with model A [MeX - -E(H) - E(H) - -XMe (E = S and Se
X = Cl and Br)]. The quantum theory of atoms-in-molecules dual functional analysis (QTAIM-DFA) is applied. The total electron energy densities Hb(rc) are plotted versus Hb(rc) - Vb(rc)/2 for the interactions at the bond critical points (BCPs
∗), where Vb(rc) show the potential energy densities at the BCPs. Data for the perturbed structures around the fully optimized structures are employed for the plots, in addition to those of the fully optimized structures. The plots were analysed using the polar coordinate (R, θ) representation of the data of the fully optimized structures. Data containing the perturbed structures were analysed by (θp, κp), where θp corresponds to the tangent line of the plot and κp is the curvature. Whereas (R, θ) shows the static nature, (θp, κp) represents the dynamic nature of interactions. E-∗-E are all classified as shared shell (S) interactions for (1)-(4) and as weak covalent (Cov-w) in nature (S/Cov-w). The nature of pure CS (closed shell)/typical-HB (hydrogen bond) with no covalency is predicted for E-∗-X in (1) and (3), regular CS/typical-HB nature with covalency is predicted for (4), and an intermediate nature is predicted for (2). The NBO energies evaluated for E-∗-X in (1)-(4) are substantially larger than those in model A due the shortened length at the naphthalene 1,8-positions. The nature of E2X2 of σ(4c-6e) is well elucidated via QTAIM-DFA. The nature of E2X2 σ(4c-6e) of the X - -E - E - -X type in 1-(8-XC10H6)E-E(C10H6X-8')-1' [(1) E, X = S, Cl
(2) S, Br
(3) Se, Cl
(4) Se, Br] is elucidated with quantum theory of atoms in molecules (QTAIM) after structural determination of (1), (3) and (4). In the case of E - -X, the nature of a typical-hydrogen bond (t-HB) with no covalency is predicted for (1) and (3), a t-HB with covalency is predicted for (4), and the t-HB seems intermediate for (2).

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Dichlorosilylene Transfer to a P-Fluorophosphaalkene: The Route to a C-Dichlorofluorosilyl-Functionalized Dialkyldiphosphene

Cristina Mitrofan, Thorsten Gust, Andreas Zanin, Roxana M. B�rzoi, Peter G. Jones, Wolf-W. du Mont, Satoko Hayashi, Waro Nakanishi, Heinrich C. Marsmann

European Journal of Inorganic Chemistry ( Wiley-VCH Verlag )  2017 ( 11 ) 1526 - 1536   2017.04  [Refereed]

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Reactions of the (trichlorosilyl)germane Me3GeSiCl3 and of the unsymmetric disilane Me3SiSiCl3 with the P-fluorophosphaalkene (Me3Si)2C=PF (1) proceed with transfer of SiCl2 (2) leading to the new C-dichlorofluorosilyl-functionalized dialkyldiphosphene (Cl2FSi)(Me3Si)2CP=PC(SiCl2F)(SiMe3)2 (6), which was characterized by X-ray crystallography. The P-phosphanylphosphaalkene (Me3Si)2C=PP[C(SiCl2F)(SiMe3)2]SiCl2F (8a) was detected in the reaction mixtures by 31P NMR spectroscopy, accompanied by its isomer 8b, presumably (Cl2FSi)(Me3Si)C=PP[C(SiCl2F)(SiMe3)2]SiMe3. The unsymmetric dimers 8a and 8b rearrange by a 1,3-(P→C) silyl group shift, providing the inversion-symmetric diphosphene 6. Compound 6 was transformed with selenium into a selenadiphosphirane (9). Quantum chemical calculations were performed on intermediates on the route from 1 and 2 to the metastable unsymmetric dimers 8a and 8b. The addition of SiCl2 to the P=C bond of 1, followed by ring opening of the silaphosphirane 4, provides the phosphinidene (Me3Si)2(Cl2FSi)CP (5), which rearranges further to isomeric P-silylphosphaalkenes (Me3Si)2C=PSiCl2F (7a) and (Cl2FSi)(Me3Si)C=PSiMe3 (7b). Rapid phosphinidene–phosphaalkene P–P coupling reactions of 5 with 7a and with 7b followed by 1,2-(P→P) silyl group shift of ylide-type dimers 11a and 11b explain the formation of the observed species 8a and 8b. The absence of species related to 8b in previous experiments on the reactions of the P-chlorophosphaalkene (Me3Si)2C=PCl (1′) with Si2Cl6, with Me3GeSiCl3, and with Me3SiSiCl3, allows us to suggest that in the P-chlorophosphaalkene case nucleophile-supported SiCl2 insertion into the P–Cl bond or the substitutive Cl–/SiCl3 – exchange are the preferred routes to the metastable P-(trichlorosilyl)phosphaalkene (Me3Si)2C=PSiCl3.

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Linear Four-Chalcogen Interactions in Radical Cationic and Dicationic Dimers of 1,5-(Dichalcogena)canes: Nature of the Interactions Elucidated by QTAIM Dual Functional Analysis with QC Calculations

Satoko Hayashi, Kengo Nagata, Shota Otsuki, Waro Nakanishi （Part： Lead author )

Journal of Physical Chemistry A ( American Chemical Society )  121 ( 12 ) 2482 - 2496   2017.03  [Refereed]

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The dynamic and static nature of extended hypervalent interactions of the BE⋯AE⋯AE⋯BE type are elucidated for four center-seven electron interactions (4c-7e) in the radical cationic dimers (1·+) and 4c-6e in the dicationic dimers (12+) of 1,5-(dichalcogena)canes (2: AE(CH2CH2CH2)2 BE: AE, BE = S, Se, Te, and O). The quantum theory of atoms-in-molecules dual functional analysis (QTAIM-DFA) is applied for the analysis. Total electron energy densities Hb(rc) are plotted versus Hb(rc) - Vb(rc)/2 [= (h2/8m)∇2ρb(rc)] at bond critical points (BCPs) of the interactions, where Vb(rc) values show potential energy densities at BCPs. Data from the fully optimized structures correspond to the static nature of the interactions. Those from the perturbed structures around the fully optimized ones are also plotted, in addition to those of the fully optimized ones, which represent the dynamic nature of interactions. The BE⋯AE-AE⋯BE interactions in 12+ are stronger than the corresponding ones in 1·+, respectively. On the one hand, for 12+ with AE, BE = S, Se, and Te, AE⋯AE are all classified by the shared shell interactions and predicted to have the weak covalent nature, except for those in 1a2+ (AE = BE = S) and 1d2+ (AE = BE = Se), which have the nature of regular closed shell (r-CS)/trigonal bipyramidal adduct formation through charge transfer (CT-TBP). On the other hand, AE⋯BE are predicted to have the nature of r-CS/molecular complex formation through charge transfer for 1a2+, 1b2+ (AE = Se
BE = S), and 1d2+ or r-CS/CT-TBP for 1c2+ (AE = Te
BE = S), 1e2+ (AE = Te
BE = Se), and 1f2+ (AE = BE = Te). The BE⋯AE-AE⋯BE interactions in 1·+ and 12+ are well-analyzed by applying QTAIM-DFA.

DOI

Behavior of Intramolecular π-π Interactions with Doubly Degenerated Bond Paths Between Carbon Atoms in Opposite Benzene Rings of Diethenodihydronaphthalenes by QTAIM Approach

Kohei Matsuiwa, Yuji Sugibayashi, Yutaka Tsubomoto, Satoko Hayashi, Waro Nakanishi

ChemistrySelect ( Wiley-Blackwell )  2 ( 1 ) 90 - 100   2017.01  [Refereed]

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Dynamic and static nature of intramolecular π-π interactions between ethylene moieties in diethenodihydronaphthanaphtalene (1 b) and derivatives (2 b–12 b) are elucidated by employing QTAIM-DFA (QTAIM dual functional analysis). During the course of the investigations, doubly degenerated bond paths were detected between carbon atoms in opposite benzene rings of dibenzo-derivative of 1 b with an etheno-bridge on the backside (11 b). It must be very curious, since one BP should correspond to an interaction between two carbon atoms. Intramolecular π-π interactions in 1 b–12 b are all classified by the pure CS (closed shell) interactions. The interactions between ethylene groups, with no substituents as in 1 b–8 b, are predicted to have the van der Waals (vdW) nature. Those for 9 b–12 b have the hydrogen bond (HB) nature with no covalency, where the ethylene moieties are included in one or two benzene ring(s), except for 10 b, if evaluated with MP2/6-311G(3d). The character in 10 b is close to the borderline area between the vdW and HB nature with no covalency, although should be the vdW type. The interactions in 2 b–12 b evaluated with MP2/6-311G(3d) are predicted to be somewhat stronger than the case with MP2/6-311G(d), as a whole.

DOI

Dynamic and Static Behavior of Intramolecular π–π Interactions in [2.2]- and [3.3]Cyclophanes, Elucidated by QTAIM Dual Functional Analysis with QC Calculations

Kohei Matsuiwa, Satoko Hayashi, Waro Nakanishi

ChemistrySelect ( Wiley-Blackwell )  2 ( 5 ) 1774 - 1782   2017.01  [Refereed]

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Dynamic and static nature of the intramolecular π–π interactions between phenyl moieties is elucidated for cyclophanes, 1,4-C6H4(CnH2n)2C6H4-1’,4’ (1 (n = 2) and 2 (n = 3)), 1,3,5-C6H3(CnH2n)3C6H3-1’,3’,5’ (3 (n = 2) and 4 (n = 3)), C6(CnH2n)6C6 (5 (n = 2) and 6 (n = 3)), and 1’,4’-C6H4(CnH2n)2-1,4-C6H2-2,5-(CnH2n)2C6H4-2’’,5’’ (7 (n = 2) and 8 (n = 3)). QTAIM-DFA (QTAIM dual functional analysis) was applied for the elucidations, together with QC calculations. While the bond paths (BPs) are detected for the intramolecular π–π interactions in 2, 4, 6, and 8, they are not detected for those in 1, 5, and 7. In the case of 3, BPs are not detected for those between the bridgehead carbon atoms of (1C, 1’C), (3C, 3’C), and (5C, 5’C), whereas they appear between the non-bridgehead carbon atoms of (2C, 2’C), (4C, 4’C), and (6C, 6’C). The intramolecular π–π interactions in the cyclophanes are all classified by the pure closed shell interactions. While the intramolecular π–π interactions in 2, 4, 6, and 8 are characterized as the vdW nature, those in 3 are predicted to have the typical HB nature without covalency. The interaction distances between (2C, 2’C), (4C, 4’C), and (6C, 6’C) in 3 are shorter than those connected by BPs, although the distances would not be the key parameters for BPs to appear in cyclophanes.

DOI

Nature of S2Se2 σ(4c–6e) at naphthalene 1,8-positions and models, elucidated by QTAIM dual functional analysis

Waro Nakanishi, Yutaka Tsubomoto, Satoko Hayashi

RSC Advances ( Royal Society of Chemistry (RSC) )  6 ( 95 ) 93195 - 93204   2016.09  [Refereed]

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<p>The nature of ^BE–*–^AE–*–^AE–*–^BE σ(4c–6e) is primarily elucidated at naphthalene 1,8-positions: while the weak covalent nature is predicted for all ^AE–*–^AE, the HB nature with covalency or the CT-MC (MC formation through CT) nature is for ^AE–*–^BE.</p>

DOI

Behavior of Halogen Bonds of the Y−X⋅⋅⋅π Type (X, Y=F, Cl, Br, I) in the Benzene π System, Elucidated by Using a Quantum Theory of Atoms in Molecules Dual-Functional Analysis

Yuji Sugibayashi, Satoko Hayashi, Waro Nakanishi

ChemPhysChem ( Wiley-VCH Verlag )  17 ( 16 ) 2579 - 2589   2016.08  [Refereed]

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The nature of halogen bonds of the Y−X-✶-π(C6H6) type (X, Y=F, Cl, Br, and I) have been elucidated by using the quantum theory of atoms in molecules (QTAIM) dual-functional analysis (QTAIM-DFA), which we proposed recently. Asterisks (✶) emphasize the presence of bond-critical points (BCPs) in the interactions in question. Total electron energy densities, Hb(rc), are plotted versus Hb(rc)−Vb(rc)/2 [=(ħ2/8m)∇2ρb(rc)] for the interactions in QTAIM-DFA, in which Vb(rc) are potential energy densities at the BCPs. Data for perturbed structures around fully optimized structures were used for the plots, in addition to those of the fully optimized ones. The plots were analyzed by using the polar (R, θ) coordinate for the data of fully optimized structures with (θp, κp) for those that contained the perturbed structures
θp corresponds to the tangent line of the plot and κp is the curvature. Whereas (R, θ) corresponds to the static nature, (θp, κp) represents the dynamic nature of the interactions. All interactions in Y−X-✶-π(C6H6) are classified by pure closed-shell interactions and characterized to have vdW nature, except for Y−I-✶-π(C6H6) (Y=F, Cl, Br) and F−Br-✶-π(C6H6), which have typical hydrogen-bond nature without covalency. I−I-✶-π(C6H6) has a borderline nature between the two. Y−F-✶-π(C6H6) (Y=Br, I) were optimized as bent forms, in which Y-✶-π interactions were detected. The Y-✶-π interactions in the bent forms are predicted to be substantially weaker than those in the linear F−Y-✶-π(C6H6) forms.

DOI

Intramolecular π–π Interactions in Diethanodihydronaphthalene and Derivatives: Dynamic and Static Behavior of the Interactions Elucidated by QTAIM Dual Functional Analysis

Kohei Matsuiwa, Satoko Hayashi, Waro Nakanishi

ChemistrySelect ( Wiley-Blackwell )  1 ( 10 ) 2344 - 2353   2016.07  [Refereed]

　View Summary

Dynamic and static behavior of the intramolecular π–π interactions between ethylene moieties in diethanodihydronaphthalene (1 a) and the derivatives (2 a–12 a) are elucidated by employing QTAIM-DFA (QTAIM dual functional analysis), which we proposed recently. Total electron energy densities Hb(rc) are plotted versus Hb(rc) – Vb(rc)/2 at bond critical points (BCPs) for the interactions in question in QTAIM-DFA, where Vb(rc) are potential energy densities at BCPs. After analysis of the plots, the π–π interactions in 1 a–12 a are all classified by the pure closed shell interactions and characterized to have the vdW nature with MP2/6-311G(d), except for those in 10 a–12 a, where the ethylene moieties in 1 a are replaced by benzene moieties. The character in 10 a–12 a is predicted to have the typical-HB (hydrogen bond) nature without covalency, although that in 10 a and 11 a seems close to the border area between the two. Indeed, the twisted structures were predicted for 1 a–4 a with MP2/6-311G(d), but the observed non-twisted structures of 1 a–3 a were better reproduced with MP2/6-311G(3d). The typical-HB nature without covalency was additionally predicted for the interactions between ethylene and benzene moieties in 9 a with MP2/6-311G(3d), maybe due to somewhat shorter C … C distances predicted for the interactions in question. The interaction in TS is also discussed exemplified by 10 a (C2v).

DOI

Quantum chemical calculations with the AIM approach applied to the π-interactions between hydrogen chalcogenides and naphthalene

Satoko Hayashi, Yuji Sugibayashi, Waro Nakanishi （Part： Lead author )

RSC Advances ( Royal Society of Chemistry (RSC) )  6 ( 55 ) 49651 - 49660   2016.04  [Refereed]

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<p>The nature of π-interactions in (EH₂)<italic>n</italic>–*–π(C₁₀H₈) (<italic>n</italic> = 1 and 2: E = O, S, Se and Te) is elucidated with QTAIM-DFA. They have the character of the vdW-<italic>nature</italic> of the <italic>pure</italic>-CS interactions, except for HHTe–*–π(C₁₀H₈), which seems stronger than others.</p>

DOI

Mechanistic Studies on the Generation and Properties of Superelectrophilic Singlet Carbenes from Bis(perfluoroalkanesulfonyl)bromonium Ylides

Kazunori Miyamoto, Susumu Iwasaki, Ryusuke Doi, Taiga Ota, Yufuko Kawano, Junpei Yamashita, Yuuta Sakai, Norihiro Tada, Masahito Ochiai, Satoko Hayashi, Waro Nakanishi, Masanobu Uchiyama

Journal of Organic Chemistry ( American Chemical Society )  81 ( 8 ) 3188 - 3198   2016.04  [Refereed]

　View Summary

Pyrolysis of bis(perfluoroalkanesulfonyl)bromonium ylides in various olefins results in highly stereospecific formation of cyclopropanes via unimolecular decomposition. Product analysis, kinetic study, substituent effects, and theoretical study revealed the generation of singlet bis(perfluoroalkanesulfonyl)carbenes stabilized by intramolecular coordination of sulfonyl oxygen.

DOI

Transannular E⋯E' Interactions in Neutral, Radical Cationic, and Dicationic Forms of cyclo-[E(CH2CH2CH2)2E'] (E, E' = S, Se, Te, and O) with Structural Feature: Dynamic and Static Behavior of E⋯E' Elucidated by QTAIM Dual Functional Analysis

Satoko Hayashi, Kohei Matsuiwa, Nozomu Nishizawa, Waro Nakanishi （Part： Lead author )

Journal of Organic Chemistry ( American Chemical Society )  80 ( 24 ) 11963 - 11976   2015.12  [Refereed]

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The nature of the transannular E-∗ -E' interactions in neutral, radical cationic, and dicationic forms of cyclo-E(CH2CH2CH2)2E' (1) (E, E' = S, Se, Te, and O) (1, 1•+, and 12+, respectively) is elucidated by applying QTAIM dual functional analysis (QTAIM-DFA). Hb(rc) are plotted versus Hb(rc) - Vb(rc)/2 for the data of E-∗ -E' at BCPs in QTAIM-DFA, where ∗ emphasizes the existence of BCP. Plots for the fully optimized structures are analyzed by the polar coordinate (R, θ) representation. Those containing the perturbed structures are by (θp, κp): θp corresponds to the tangent line of the plot, and κp is the curvature. While (R, θ) describes the static nature, (θp, κp) represents the dynamic nature of interactions. The nature is well-specified by (R, θ) and (θp, κp). E-∗ -E' becomes stronger in the order of 1 &lt
1•+ &lt
12+, except for O-∗ -O. While E-∗ -E' (E, E' = S, Se, and Te) in 12+ are characterized as weak covalent bonds, except for S-∗ -Te (MC nature through CT) and Se-∗ -Te (TBP nature through CT), O-∗ -E' seems more complex. The behavior of E-∗ -E' in 12+ is very close to that of cyclo-E(CH2CH2CH2)E' (E, E' = S, Se, Te, and O), except for O-∗ -O.

DOI

Dynamic and static behavior of the H⋯π and E⋯π interactions in EH2 adducts of benzene π-system (E = O, S, Se and Te), elucidated by QTAIM dual functional analysis

Satoko Hayashi, Yuji Sugibayashi, Waro Nakanishi （Part： Lead author )

Physical Chemistry Chemical Physics ( Royal Society of Chemistry (RSC) )  18 ( 15 ) 9948 - 9960   2015.12  [Refereed]

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<p>The nature of the π-HB and π-EB interactions are elucidated for (EH₂)-*-π(C₆H₆) (E = O, S, Se and Te) with QTAIM-DFA. All the interactions were classified by the pure CS interactions and characterized as the vdW nature, with the suggestion of stronger π-EBs relative to π-HBs.</p>

DOI

Dynamic and static behavior of hydrogen bonds of the X–H⋯π type (X = F, Cl, Br, I, RO and RR′N; R, R′ = H or Me) in the benzene π-system, elucidated by QTAIM dual functional analysis

Yuji Sugibayashi, Satoko Hayashi, Waro Nakanishi

Physical Chemistry Chemical Physics ( Royal Society of Chemistry (RSC) )  17 ( 43 ) 28879 - 28891   2015.10  [Refereed]

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<p>The nature of the X–H-*-π interactions in X–H-*-π(C₆H₆) (X = F, Cl, Br, I, HO, MeO, H₂N, MeHN and Me₂N) was elucidated by applying QTAIM dual functional analysis. The interactions were all classified by pure closed-shell interactions and characterized to have the vdW nature.</p>

DOI

Basic Concept and Applications of AIM Dual Functional Analysis: For Better Understanding and Explanation of Experimental Results Related to Interactions

Satoko Hayashi, Waro Nakanishi （Part： Lead author )

Journal of Synthetic Organic Chemistry, Japan ( The Society of Synthetic Organic Chemistry, Japan )  73 ( 1 ) 39 - 52   2015.02  [Refereed]

DOI

Dynamic and static behavior of the E–E′ bonds (E, E′ = S and Se) in cystine and derivatives, elucidated by AIM dual functional analysis

Yutaka Tsubomoto, Satoko Hayashi, Waro Nakanishi

RSC Advances ( Royal Society of Chemistry (RSC) )  5 ( 15 ) 11534 - 11540   2015.01  [Refereed]

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<p>AIM-DFA (AIM dual functional analysis) is applied to the E–E′ bonds (E, E′ = S and Se) in <italic>R</italic>-cystine (<bold>1</bold>), its derivatives and MeEE′Me. The nature of E–E′ is elucidated by (<italic>θ</italic>_p, <italic>κ</italic>_p: dynamic behavior) and (<italic>R</italic>, <italic>θ</italic>: static behavior), through AIM-DFA.</p>

DOI

Dynamic and static behavior of E-E' bonds in neutral and charged forms of HEE'H, MeEE'Me, and Cyclo-1,2-EE'(CH2)3 (E, E' = O, S, Se, and Te) elucidated by AIM dual functional analysis

Satoko Hayashi, Kohei Matsuiwa, Hiroaki Miza, Waro Nakanishi （Part： Lead author )

Heteroatom Chemistry ( Wiley-Blackwell )  25 ( 5 ) 449 - 472   2014.11  [Refereed]

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The nature of the E-∗-E' bonds in neutral, monoanionic, monocationic, and dicationic forms of HEE'H (1), MeEE'Me (2), and cyclo-1,2-EE'(CH2)3 (3) (E, E' = O, S, Se, Te) is investigated by applying AIM (atoms-in-molecules method) dual functional analysis. Hb(rc) are plotted versus Hb(rc) - Vb(rc)/2 for the data of E-∗-E' at bond critical points (BCPs) of fully optimized structures and perturbed structures around the fully optimized ones. Plots for the fully optimized structures are analyzed by the polar coordinate (R, θ) representation. The (θp, κp) parameters are derived from those of the perturbed structures: θp corresponds to the tangent line of each plot, and κp is the curvature. While (R, θ) correspond to the static nature, (θp, κp) represent the dynamic nature of interactions. The nature of E-∗-E' in the neutral and charged species is classified by comparing their θ and θp values with those of the standard interactions as a reference. Data for E-∗-E' in the neutral forms of 1-3 appear in the shared-shell (SS) region (180° &lt
θ), except for MeS-∗-TeMe (2c), which does in the regular closed-shell (CS) region (90°&lt
θ &lt
180°). The E-E' bonds in the monoanionic forms of 1-3 become much longer and weakened. Therefore, data of the monoanionic forms appear in the regular CS. On the other hand, the strengths of E-∗-E' in the mono- and dicationic forms are almost equal to those in the neutral forms of 1-3 in the plots, irrespective of the shorter E-∗-E' lengths in the cationic forms, relative to the neutral forms.

DOI

Aromatic selenoic,selenothioic,and diselenoic acid salts:isolation, characterization, and 77senmr spectra,together with theoretical elucidation

Toshiaki Murai, Daisuke Nishi, Satoko Hayashi, Waro Nakanishi

Bulletin of the Chemical Society of Japan ( Chemical Society of Japan )  87 ( 6 ) 677 - 692   2014  [Refereed]

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To systematically elucidate molecular and electronic structures of aromatic selenoic acid salts and their heavier congeners, they were synthesized by reacting selenoic, selenothioic, and diselenoic acid Se-[2-(trimethylsilyl) ethyl] esters with ammonium fluorides. The resulting salts were characterized by 13C and 77SeNMR spectra, and some of their molecular structures were disclosed by X-ray analyses. These results were compared with spectroscopic properties and molecular structures of selenoic and selenothioic acid Se-methyl esters. As a result, in the resonance hybrids of selenoic and selenothioic acid ammonium salts, the resonance structures involving carbonselenium double bonds also contribute to the resonance hybrids, and the importance of these resonance structures appears to increase on going from selenoic to selenothioic acid salts on the basis of the results of the coupling constants of carbonselenium bonds and UVvisible spectra. The results were well supported by the optimized structures and evaluated NMR parameters for the species. © 2014 The Chemical Society of Japan.

DOI

Photoinduced regio-and stereoselective introduction of phenylchalcogeno moieties to ethynylferrocene

Akihiro Nomoto, Satoko Hayashi, Takuya Fujiyama, Takuma Ikeda, Kiichi Hirata, Jun Tohoma, Kiyomi Kakiuchi, Waro Nakanishi, Akiya Ogawa

Bulletin of the Chemical Society of Japan ( Chemical Society of Japan )  87 ( 4 ) 550 - 552   2014  [Refereed]

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Upon photoirradiation, diphenyl diselenide and diphenyl ditelluride reacted with ethynylferrocene to afford the corresponding bischalcogenated vinylferrocenes. Regioand stereoselectivities were determined by X-ray crystal analysis, and redox properties were investigated by cyclic voltammetry. © 2014 The Chemical Society of Japan.

DOI

Relativistic effects on the 125Te and 33S NMR chemical shifts of various tellurium and sulfur species, together with 77Se of selenium congeners, in the framework of a zeroth-order regular approximation: applicability to tellurium compounds

Satoko Hayashi, Kohei Matsuiwa, Waro Nakanishi （Part： Lead author )

RSC Adv. ( Royal Society of Chemistry (RSC) )  4 ( 84 ) 44795 - 44810   2014  [Refereed]

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<p>The relativistic effects on <italic>σ</italic>(Te), <italic>σ</italic>(Se), and <italic>σ</italic>(S) were evaluated separately by scalar and spin–orbit terms for various species containing Te, Se, and S nuclei. The applicability of <italic>σ</italic>^t(Te)_Rlt-so to analyze <italic>δ</italic>(Te)_obsd and the trend in the nuclei are discussed.</p>

DOI

Dynamic behavior of hydrogen bonds from Pure closed shell to shared shell interaction regions elucidated by AIM dual functional analysis

Satoko Hayashi, Kohei Matsuiwa, Masayuki Kitamoto, Waro Nakanishi （Part： Lead author )

Journal of Physical Chemistry A ( American Chemical Society (ACS) )  117 ( 8 ) 1804 - 1816   2013  [Refereed]

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The dynamic behavior of hydrogen bonds (HBs) was clarified for the wide range of interactions applying AIM dual functional analysis. Plots of H b(rc) versus Hb(rc) - V b(rc)/2 are analyzed in the polar (R, θ) representation, where Hb(rc) and Vb(r c) are total electron and potential energy densities at bond critical points, respectively, for the fully optimized structures. Data of the fully optimized structure and four perturbed ones around it are plotted for each interaction, which give a specific curve. The curve is analyzed by (θp, κp): θp corresponds to the tangent line from the y-direction and κp is the curvature. Whereas (R, θ) correspond to the static nature, (θp, κp) represent the dynamic nature of interactions. Indeed, HBs can be classified only by one parameter of θ, but θp supplies more information necessary for better understanding of HBs. Although H2Se-*-HSeH and H3N-*-HNH2 show the nature of pure CS (closed shell) of the vdW-type, H2S-*-HSH and H2O-*-HOH contain the nature of pure CS other than the vdW-type (HB-typical). The regular CS nature is observed for B-*-HF (B = HF, H2Se, H2S, H2O, and H2C=O). The HF-*-HF interaction is described as HB-typical, whereas others are by CTMC-type. The nature of H3N-*-HX (X = F, Cl, Br) is regular CS of the CTTBP-type. HBs in charged species, such as [HOH-*-OH]- and [H2O-*-H-*-OH 2]+, show the weak covalent nature of SS (shard shell). The dynamic behavior of HBs helps us to understand HBs in more detail, in addition to the static behavior. © 2013 American Chemical Society.

DOI

Experimental and theoretical advances in functional understanding of flavonoids as anti-tumor agents

Bandarugattu V. Babu, Naveen K. Konduru, Waro Nakanishi, Satoko Hayashi, Naseem Ahmed, Petar M. Mitrasinovic

Anti-Cancer Agents in Medicinal Chemistry ( Bentham Science Publishers Ltd. )  13 ( 2 ) 307 - 332   2013  [Refereed]

　View Summary

The potential of flavonoids to act as anti-tumor agents has been recognized but not fully understood because flavonoids are acting at several stages in cancer progression with distinct structure-function relationships. A whole family of structurally different flavonoids is herein described by reviewing some critical aspects of their pro-oxidant behavior in vitro/vivo and in cell systems by which they may work as antioxidants. Different classes of flavonoids (chalcones, flavones, isoflavones, flavanols, flavanones and anthocyanins) are synthetically mimicked using natural product structure-antioxidant activity relationships that are relevant for their enhanced function against cancer as well as severe inflammation conditions under which an increased oxidative stress is often implicated. In the context of the common mechanisms of flavonoid action, clinical data on benefits of flavonoids in fighting against cancer are discussed. A structural basis needed to improve antioxidant activity of these agents is elaborated in more detail. © 2013 Bentham Science Publishers.

DOI

Role of dG/dw and dV/dw in AIM analysis: An approach to the nature of weak to strong interactions

Waro Nakanishi, Satoko Hayashi

Journal of Physical Chemistry A ( American Chemical Society (ACS) )  117 ( 8 ) 1795 - 1803   2013  [Refereed]

　View Summary

Role of dGb(rc)/dw and dVb(r c)/dw is revealed as the basic atoms-in-molecules (AIM) functions to evaluate, classify, and understand the nature of interactions, as well as G b(rc) and Vb(rc). The border area between van der Waals (vdW) adducts and hydrogen-bonded (HB) adducts is shown to appear at around dGb(rc)/dw = -dVb(r c)/dw and that between molecular complexes (MC) and trigonal bipyramidal adducts (TBP) of chalcogenide dihalides appears at around 2dG b(rc)/dw = -dVb(rc)/dw. H b(rc) are plotted versus Hb(rc) - Vb(rc)/2 at bond critical points (BCPs) in the AIM dual functional analysis. The plots incorporate the classification of interactions by the signs of ∇2ρb(rc) and H b(rc). R [= (x2 + y2)1/2] corresponds to the energy for the interaction in question at BCPs, where (x, y) = (Hb(rc), Hb(rc) - V b(rc)/2) and (x, y) = (0, 0) at the origin. The segment of lines for the plots (S) should correspond to energy, if the segment is substantially linear. The first derivative of S (dS) is demonstrated to be proportional to R. Relations between AIM functions, such as dV b(rc)/dw, dGb(rc)/dw, dH b(rc)/d[Hb(rc) - V b(rc)/2], d2Vb(rc)/ dw2, d2Gb(rc)/dw2, and d2Hb(rc)/d[Hb(rc) - Vb(rc)/2]2, are also discussed. The results help us to understand the nature of interactions. © 2013 American Chemical Society.

DOI

Unusual Saddle-like Structure of (2-MeOC6H4CS)2S: Theoretical Studies and Comparison with its Oxygen Isologues

Osamu Niyomura, Yuka Kito, Shinzi Kato, Masaru Ishida, Masahiro Ebihara, Satoko Hayashi, Waro Nakanishi

Zeitschrift für anorganische und allgemeine Chemie ( Wiley )  638 ( 15 ) 2508 - 2520   2012.12  [Refereed]

DOI

Applications of Normal Coordinates of Internal Vibrations to Generate Perturbed Structures: Dynamic behavior of weak to strong interactions elucidated by atoms-in-molecules dual functional analysis

Waro Nakanishi, Satoko Hayashi, Kohei Matsuiwa, Masayuki Kitamoto

Bulletin of the Chemical Society of Japan ( The Chemical Society of Japan )  85 ( 12 ) 1293 - 1305   2012  [Refereed]

　View Summary

Normal coordinates of internal vibrations (NIV) are employed to generate the perturbed structures necessary in the atoms-in-molecules (AIM) dual functional analysis for a wide range of weak to strong interactions. Hb(rc) are plotted versus Hb(rc) VΔ(rc)/2 (h2/8m)r2μb(rc)] at bond critical points in the treatment, which incorporates the classification of interactions by signs of r2μb(rc) and Hb(rc). The plots are analyzed using the polar (R) representation. Each plot for an interaction shows a specific curve, which is expressed by (p, ): p corresponds to the tangent line for the plot measured from the y-direction and p is the curvature. While (R) correspond to the static behavior of interactions at the fully optimized structures, (p,p) exhibit the dynamic nature. The (p, ) values evaluated employing the perturbed structures with NIV are shown to be very close to those obtained using perturbed structures partially optimized with the distances in question being fixed suitably (POM). The magnitudes of differences in p and between those evaluated with NIV and POM are 2° and 2 au-1, respectively, for usual interactions. It is demonstrated that NIV is applicable to wide range of usual interactions, as well as POM. © 2012 The Chemical Society of Japan.

DOI

Role of p(Z)–π(Ar/Nap) conjugation in structures of 1-(arylchalcogena)naphthalenes for Z = Te versus Se, S and O: experimental and theoretical investigations

Takahito Nakai, Mitsuhiro Nishino, Satoko Hayashi, Masato Hashimoto, Waro Nakanishi

Dalton Transactions ( Royal Society of Chemistry (RSC) )  41 ( 25 ) 7485 - 7485   2012  [Refereed]

DOI

Dynamic and static behaviors of N-Z-N σ(3c-4e) (Z = S, Se, and Te) interactions: Atoms-in-molecules dual functional analysis with high-resolution X-ray diffraction determination of electron densities for 2-(2-pyridylimino)-2 H -1,2,4-thiadiazolo[2,3- a ]pyridine

Waro Nakanishi, Satoko Hayashi, Mateusz B. Pitak, Michael B. Hursthouse, Simon J. Coles

Journal of Physical Chemistry A ( American Chemical Society (ACS) )  115 ( 42 ) 11775 - 11787   2011.10  [Refereed]

　View Summary

The structure of 2-(2-pyridylimino)-2H-1,2,4-thiadiazolo[2,3-a]pyridine (NSN) indicates that the molecule has a planar geometry with a linear N⋯S⋯N linkage, creating a tetracyclic structure of the formal C2v symmetry. To clarify the nature of the NSN σ(3c-4e) bonding, together with the related NSeN and NTeN, the dynamic and static behaviors are investigated by applying atoms-in-molecules (AIM) dual functional analysis to both the fully optimized and perturbed structures. The structures were optimized computationally, retaining C2v symmetry. All bond critical points are detected as expected and exhibited on both sides of the N⋯Z⋯N moiety which supports the formation of NZN σ(3c-4e). It is confirmed that N⋯S⋯N is of the covalent nature close to Me2S+-*-Cl or Me2Se+-*- Br, whereas N⋯Se⋯N and N⋯Te⋯N have the (regular) CS nature close to the CT adducts of Me2S(-*-Cl)2 (TBP) and Me2Se-*-Br2 (MC), respectively. An experimental high-resolution charge density determination has been performed on NSN, which thoroughly supports the theoretical results. Very similar results are obtained in the analogous pyrimidyl derivatives for N⋯S⋯N, N⋯Se⋯N, and N⋯Te⋯N. AIM dual functional analysis, as validated by experimental high-resolution charge densities, is thus confirmed to be an excellent method to elucidate the nature of these interactions. © 2011 American Chemical Society.

DOI

Relativistic Effect on77Se NMR Chemical Shifts of Various Selenium Species in the Framework of Zeroth-Order Regular Approximation

Waro Nakanishi, Satoko Hayashi, Yoshifumi Katsura, Masahiko Hada

The Journal of Physical Chemistry A ( American Chemical Society (ACS) )  115 ( 31 ) 8721 - 8730   2011.08  [Refereed]

DOI

Highly regioselective amination of unactivated alkanes by hypervalent sulfonylimino-δ3-bromane

Masahito Ochiai, Kazunori Miyamoto, Takao Kaneaki, Satoko Hayashi, Waro Nakanishi

Science ( American Association for the Advancement of Science (AAAS) )  332 ( 6028 ) 448 - 451   2011.04  [Refereed]

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Amination of alkanes has generally required metal catalysts and/or high temperatures. Here we report that simple exposure of a broad range of alkanes to N-triflylimino-δ3-bromane 1 at ambient temperature results in C-H insertion of the nitrogen functionality to afford triflyl-substituted amines in moderate to high yields. Marked selectivity for tertiary over secondary C-H bonds was observed
primary (methyl) C-H bonds were inert. Addition of hexafluoroisopropanol to inhibit decomposition of 1 dramatically improved the C-H amination efficiencies. Second-order kinetics, activation parameters (negative activation entropy), deuterium isotope effects, and theoretical calculations suggest a concerted asynchronous bimolecular transition state for the metal-free C-H amination event.

DOI

Synthesis, structures and ab initio studies of selenium and tellurium bis(carbodithioates and carbothioates)

Shinzi Kato, Kazuyasu Tani, Masaru Ishida, Junko Nonogaki, Masahiro Ebihara, Satoko Hayashi, Waro Nakanishi, Osamu Niyomura, Fumio Ando, Jugo Koketsu

Dalton Transactions ( Royal Society of Chemistry (RSC) )  40 ( 32 ) 8156 - 8169   2011  [Refereed]

DOI

How Do Weak Z-X-X and Stronger X-Z-X Interactions Affect NMR Chemical Shifts of Chalcogenide Dihalides, R(2)Z center dot X-2? Theoretical Background on the Structural Prediction of R(2)Z center dot X-2 through Chemical Shifts in Solutions

Akito Tanioku, Takahito Nakai, Satoko Hayashi, Waro Nakanishi

HETEROATOM CHEMISTRY ( WILEY-BLACKWELL )  22 ( 3-4 ) 446 - 456   2011  [Refereed]

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The mechanism is clarified for the high applicability of criteria to distinguish molecular complexes (MC) from pseudo-trigonal bipyramidal adducts (TBP) of chalcogenide dihalogens in solutions, based on the NMR chemical shifts. The criteria are theoretically investigated employing MC and TBP of MeSeMe (1), EtSeEt (3), PhSePh (7), PhSPkt (8), and PhSeH (22) with chlorine and/or bromine. The adducts of (CH2=CH)(2)Se (26), H2C(CH=CH)(2)Se (27), and H2C(CH=CH)(2)S (28) are also investigated. Behaviors of total absolute magnetic tensors (sigma(t)) for the atoms in question are analyzed separately by the diamagnetic and paramagnetic terms, which well sup-port the observed NMR chemical shifts of the MC and TBP adducts in solutions. As a result, the criteria are thoroughly supported on the basis of theoretical background and the mechanism of criteria is clarified with the diamagnetic and paramagnetic terms. The results shed light on the specific effect of weak Z-X-X and stronger X-Z-X interactions on the NMR chemical shifts of the adducts, R(2)Z center dot X-2. (C) 2011 Wiley Periodicals, Inc. Heteroatom Chem 22:446-456,2011; View this article online at wileyonlinelibrary.com. DOI 10.1002/hc.20707

DOI

How do weak Z-X-X and stronger X-Z-X interactions affect NMR chemical shifts of chalcogenide dihalides, R2Z·X2? Theoretical background on the structural prediction of R2Z·X2 through chemical shifts in solutions

Akito Tanioku, Takahito Nakai, Satoko Hayashi, Waro Nakanishi

Heteroatom Chemistry ( Wiley )  22 ( 3-4 ) 446 - 456   2011  [Refereed]

DOI

Synthesis, structural, spectroscopic and electrochemical studies of carborane substituted naphthyl selenides

Olexandr Guzyr, Clara Viñas, Hideki Wada, Satoko Hayashi, Waro Nakanishi, Francesc Teixidor, Alberto V. Puga, Vasile David

Dalton Transactions ( Royal Society of Chemistry (RSC) )  40 ( 13 ) 3402 - 3402   2011  [Refereed]

DOI

Imination of sulfides and sulfoxides with sulfonylimino- λ3-bromane under mild, metal-free conditions

Masahito Ochiai, Masao Naito, Kazunori Miyamoto, Satoko Hayashi, Waro Nakanishi

Chemistry - A European Journal ( Wiley )  16 ( 29 ) 8713 - 8718   2010.08  [Refereed]

　View Summary

Exposure of sulfides and sulfoxides to trifluoromethanesulfonylimino(aryl)- λ3-bromane in dichloromethane at 0°C results in a facile transfer of the sulfonylimino group to sulfur atoms and affords N-triflylsulfilimines and -sulfoximines in high yields under transition-metal-free conditions. Imination of (R)-methyl p-tolyl sulfoxide proceeded with predominant retention of configuration at the stereogenic sulfur center. The Hammett plot afforded ρ values of -0.58 for para-substituted thioanisoles and -0.49 for their equivalent sulfoxides, which suggests a buildup of positive charge on the sulfur atoms of sulfides and sulfoxides in the transition state. Calculations suggest a bimolecular nucleophilic-substitution mechanism on the negatively charged nitrogen atom of the sulfonylimino- λ3-bromane, which involves the attack of a sulfide from the opposite side to bromine(III). © 2010 Wiley-VCH Verlag GmbH &amp
Co. KGaA, Weinheim.

DOI

Dynamic behaviors of interactions: Application of normal coordinates of internal vibrations to AIM dual functional analysis

Waro Nakanishi, Satoko Hayashi

Journal of Physical Chemistry A ( American Chemical Society (ACS) )  114 ( 27 ) 7423 - 7430   2010.07  [Refereed]

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A method to evaluate the dynamic nature of interactions is proposed based on the AIM dual functional analysis. Normal coordinates of internal vibrations (NIV) are employed to generate the perturbed structures necessary for the analysis. Hb(rc) are plotted versus Hb(r c) - Vb(rc)/2 [= (h2/8m) ∇2ρb(rc)] at bond critical points for the purpose. The plots are represented by the polar (R, θ) coordinate. Each plot for an interaction shows a specific curve, which is expressed by (θp, κp): θp corresponds to the tangent line for the plot from the y-direction, and κp is the curvature. Although (R, θ) values correspond to the static nature of interactions, (θp, κp) values show the dynamic nature. The applicability of NIV is examined exemplified by the charge-transfer interactions as the first step to analyze the dynamic behaviors of interactions with NIV. The (θp, κp) values evaluated with NIV are very close to those obtained by the partial-optimization method (POM), where the distances or angles in question are fixed suitably, if the internal vibrations are substantially located on the interactions in question. The magnitudes of differences in θp and κp between those evaluated with NIV and POM are ≤2° and ≤2 au-1, respectively, for usual interactions. The treatment is demonstrated to be applicable to a wide range of interactions. © 2010 American Chemical Society.

DOI

Hypervalent λ3-bromane strategy for Baeyer-Villiger oxidation: Selective transformation of primary aliphatic and aromatic aldehydes to formates, which is missing in the classical Baeyer-Villiger oxidation

Masahito Ochiai, Akira Yoshimura, Kazunori Miyamoto, Satoko Hayashi, Waro Nakanishi

Journal of the American Chemical Society ( American Chemical Society (ACS) )  132 ( 27 ) 9236 - 9239   2010.07  [Refereed]

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A conceptually distinct, modern strategy for Baeyer-Villiger oxidation (BVO) was developed. Our novel method involves initial hydration of water to carbonyl compounds, followed by ligand exchange of hypervalent aryl-λ3-bromane on bromane(III) with the resulting hydrate, yielding a new type of activated Criegee intermediate. The intermediate undergoes BV rearrangement and produces an ester via facile reductive elimination of an aryl-λ3-bromanyl group, because of the hypernucleofugality. The novel strategy makes it possible to induce selectively the BV rearrangement of straight chain primary aliphatic as well as aromatic aldehydes, which is missing in the classical BVO: for instance, octanal and benzaldehyde afforded rearranged formate esters with high selectivity (&gt
95%) under our conditions, while the attempted classical BVO produced only carboxylic acids. This firmly establishes the powerful nature of new methodology for BVO. © 2010 American Chemical Society.

DOI

P(O, S, Se, and Te)-π(Ar) conjugations as factors to control fine structures of 1-(chalcogena)naphthalenes

Takahito Nakai, Satoko Hayashi, Waro Nakanishi

Phosphorus, Sulfur and Silicon and the Related Elements ( Informa UK Limited )  185 ( 5-6 ) 1031 - 1045   2010.05  [Refereed]

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The p(Z)-π(Ar) conjugation as the factors to control the fine structures of organic chalcogen compounds are investigated. The structures of 1-(arylchalcogena)naphthalenes [1-(p-YC6H4Z)C 10H7, 1-ArZNap
1 (Z = O) and 2 (Z = S)] are determined by the X-ray crystallographic analysis. The structures of 1, 2, and 1-ArTeNap (4) are also determined in solutions, together with 1-ArSeNap (3), employing the NMR data of 9-(arylselanyl)anthracenes (5) and 1-(arylselanyl)anthraquinones (6). NMR data of 5 and 6 can be used as the standard of the A and B structures, respectively, for all Y examined in solutions: The Se-CAr bond in 5 (A) is placed almost perpendicular to the anthryl plane in A, and the bond is located on the plane in 6 (B). Structures of 1-4 are A if Y are electronically accepting groups such as Y = Cl, but they are B with Y of donating groups such as Y = OMe both in crystals and solutions. It is interesting that δ(Ci: 1-4) are hardly affected from the conformation around the Z-CAr bonds, whereas δ(H: 1-4) and δ(Se: 3) change depending on the conformation, which enables us to determine the conformations. Copyright © Taylor &amp
Francis Group.

DOI

Atoms-in-molecules dual functional analysis of weak to strong interactions

Waro Nakanishi, Satoko Hayashi

Current Organic Chemistry ( Bentham Science Publishers Ltd. )  14 ( 2 ) 181 - 197   2010.01  [Refereed]

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Atoms-in-molecules (AIM) dual functional analysis is reviewed after brief introduction of AIM. Total electron energy densities (Hb(rc)) are plotted versus Laplacian of electron densities (▶2ρb(rc)) at bond critical points (BCPs). The plots draw a helical stream as a whole. For the better understanding of weak to strong interactions, polar coordinate (R, θ) representation is employed for the plot of Hb(rc) versus (h2/8m)▶2ρb(rc). Both x-and y-axes are expressed in the common unit of energy in this treatment: Hb(rc) = Gb(rc) + Vb(rc) and (h2/8m)▶2ρb(rc) = Hb(rc)-Vb(rc)/2 where Gb(rc) and Vb(rc) are kinetic energy densities and potential energy densities, respectively. Interactions examined are those in van der Waals adducts, hydrogen bonded complexes, molecular complexes and hypervalent adducts through charge-transfer, and some classical covalent bonds. Data employed for the plots are calculated at BCPs for full-optimized structures and optimized structures with the fixed distances r around the full-optimized distances, ro: r = ro + wao where ao is the Bohr radius with w = ±0.1 and ±0.2. The helical stream is well described by (R, Θ): R is given in the energy unit and Θ in degree is measured from the y-axis. The ratio of Vb(rc)/Gb(rc) (= k) controls Θ of which acceptable range is 45.0° &lt
Θ &lt
206.6°. Each plot for an interaction gives a curve, which supplies important information. It is expressed by Θp and κp: Θp corresponds to the tangent line measured from the y-direction and κp is the curvature of the plot at w = 0. The treatment enables us to classify, evaluate, and understand well the weak to strong interactions. © 2010 Bentham Science Publishers Ltd.

DOI

Hypervalent N-sulfonylimino-λ3-bromane: active nitrenoid species at ambient temperature under metal-free conditions

Masahito Ochiai, Kazunori Miyamoto, Satoko Hayashi, Waro Nakanishi

Chem. Commun. ( Royal Society of Chemistry (RSC) )  46 ( 4 ) 511 - 521   2010  [Refereed]

DOI

Polar coordinate representation of Hb(rc) versus (ℏ2/8m)∇2ρb(rc) at BCP in AIM analysis: Classification and evaluation of weak to strong interactions

Waro Nakanishi, Satoko Hayashi, Kenji Narahara

Journal of Physical Chemistry A ( American Chemical Society (ACS) )  113 ( 37 ) 10050 - 10057   2009.09  [Refereed]

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Polar coordinate (R, θ) representation is proposed for the plot of Hb(rc) versus (ℏ2/8m) ∇2ρb(rc) in AIM analysis to classify, evaluate, and understand weak to strong interactions in a unified way and in more detail
Hb(rc) and ∇2ρ b(rc) are total electron energy densities and the Laplacian of ρb(rc) at bond critical points (BCPs: rc), respectively, where ρb(rc) are electron densities at rc. Both the x- and y-axes of the plot are expressed in the common unit of energy since Hb(rc) = Gb(rc) + Vb(rc) and (ℏ2/8m) ∇2ρb(rc) = Hb(rc) - Vb(rc)/2 (= G b(rc) + Vb(rc)/2), where G b(rc) and Vb,(rc) are kinetic energy densities and potential energy densities, respectively. Data employed for the plot are calculated at BCPs for full-optimized structures and optimized structures with the fixed distances (r) of r = ro + wao, where ro are the full-optimized distances, ao is the Bohr radius, and w = ±0.1 and ±0.2. The plot draws a helical stream starting from near origin (Hb(rc) = (ℏ2/ 8m) ∇2ρb(rc) = 0) for very weak interactions and turns to the right as interactions become stronger. The helical stream is well described by the polar coordinate representation with (R, θ)
R is given in the energy unit, and θ in degrees is measured from the y-axis. The ratio of Vb,(rc)/Gb,(r c) (= k) controls θ, of which an acceptable range in the plot is 45.0 &lt
θ &lt
206.6°. Each plot for an interaction gives a curve, which supplies important information. It is expressed by θP and Kp
θP corresponds to the tangent line measured from the y-direction, and Kp is the curvature of the plot at w = 0. The polar coordinate (R, θ) representation with (θP, Kp) helps us to classify, evaluate, and understand the nature of weak to strong interactions in a unified way. © 2009 American Chemical Society.

DOI

Evidence for effective p(Z)-π(Ar) conjugations (Z = S, Se, and Te, as well as Z = O) in 9-(Arylchalcogenyl)triptycenes: Experimental and theoretical investigations

Satoko Hayashi, Takashi Nakamoto, Mao Minoura, Waro Nakanishi （Part： Lead author )

Journal of Organic Chemistry ( American Chemical Society (ACS) )  74 ( 13 ) 4763 - 4771   2009.07  [Refereed]

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(Chemical Equation Presented) The p(Z)-π(Ar) conjugations must operate fully in the ground states of 9-(arylchalcogenyl)triptycenes (p-YC 6H4ZTpc:1 (Z = O), 2 (Z = S), 3 (Z = Se), and 4 (Z = Te)), where the p-YC6H4 group is placed in the bisected area between two phenyl planes of the triptycyl group with the parallel orientation. The ground-state geometries, which we call (A: pl), are confirmed by X-ray analysis. However, the conjugations never operate in the transition states between (A: pl) and/or the topomeric structures (A′: pl′), where the Z-CTpc bond is perpendicular to the plane. The site-exchange processes correlate to the conjugations. Temperature-dependent 1H NMR spectra are analyzed for 2 and 3 to demonstrate the effective p(Z)-π(Ar) conjugations. The activation energies for the interconversion between (A: pl) and (A′: pl′) (GR: gear process) were obtained for 2 (ΔG ‡GR(2)) and 3 (ΔG‡ GR(3)). ΔG‡GR(3) correlate well with ΔG‡GR(2), and ΔG ‡GR(2) are well analyzed by the Hammett-type dual parameters. ΔG‡GR(2) and ΔG ‡GR(3) are demonstrated to be controlled by the resonance interaction of the p(Z)-π(C6H4)-p(Y) conjugations. QC calculations are performed on the ground and exited states of 1-4, which clarify the effective p(Z)-π(C6H4)-p(Y) conjugations for Z of heavier atoms. © 2009 American Chemical Society.

DOI

H/D isotope effect on 77Se NMR chemical shifts in 8-Methyl-1-(arylselanyl) naphthalenes and related selenides: Nonbonded C-H-Se through-space versus through-bond mechanisms

Satoko Hayashi, Kentaro Yamane, Waro Nakanishi （Part： Lead author )

Phosphorus, Sulfur and Silicon and the Related Elements ( Informa UK Limited )  184 ( 6 ) 1481 - 1495   2009.06  [Refereed]

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77Se NMR chemical shifts of methyl-d3 derivatives of 8-methyl-1- (phenylselanyl) naphthalene (1) and 8-methyl-1-(p-anisylselanyl)naphthalene (2) are observed 0.25 and 0.20 ppm upfield from 1 and 2, respectively. The observations must be the reflection of the nonbonded interactions of the C-H-Se 3c-4e type in 1 and 2. The mechanism is elucidated by means of crystallographic and theoretical investigations. The nonbonded distance between Se and CMe (2.989Å) is observed to be shorter than the sum of the van der Waals radii of the two by 0.91Å in 2. 1 and 2 may be in equilibrium between conformers A and B in solution, where Se-Ci is perpendicular to the naphthyl plane in A and it is on the plane in B. Natural bond orbital (NBO) analysis on 1 revealed that the nonbonded np(Se)-σ *(CH) interaction contributes in A, whereas nonbonded ns(Se)-σ *(C-H) and double (C-H)-σ *(Se-C) interactions operate in B.

DOI

How are non-bonded G. . .Z (Z = O, S, and Se) distances at benzene 1,2-, naphthalene 1,8-, and anthracene 1,8,9-positions controlled? An approach to causality in weak interactions

Satoko Hayashi, Waro Nakanishi （Part： Lead author )

Bulletin of the Chemical Society of Japan ( The Chemical Society of Japan )  82 ( 6 ) 712 - 722   2009  [Refereed]

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Mechanisms operating in weak interactions are sometimes quite different from those in strong ones. Factors to control the non-bonded G£Z (Z = O, S, and Se) distances at naphthalene 1,8-positions in 8-G-1-RZC10H6 are analyzed as an example to clarify the causality of weak interactions. Structures around Z in 8-G-1-RZC 10H 6 are well explained by three types, A, B, and C, where the ZCR bond is perpendicular to the naphthyl plane in A, it is placed on the plane in B, and C is intermediate between A and B. The r(Z£Z) distances in 1,8-(RZ)2C 10H 6 are observed to increase in an order of BB &lt
CC &lt
AB &lt
AA. It seems difficult to explain the sequence based on the magnitudes of the closed-shell Z£Z interactions, since the BB interaction must not be so strong especially for Z of heavier atoms. The mechanism to control the r(Z£Z) distances is demonstrated to be the reflection from the repulsive interactions between R and H at the 2-position in 1,8-(RZ) 2C 10H 6. Similar phenomena are also detected in the observed and calculated results at the benzene 1,2-, anthracene 1,8,9-, and anthraquinone 1,8,9-positions, which are explained based on the mechanism. Proposed idea and mechanism will help us to understand what happens in such weak interactions. © 2009 The Chemical Society of Japan.

DOI

Fine Structures of 8-G-1-(p-YC6H4C ≡ CSe)C10H6(G = H, Cl, and Br) in Crystals and Solutions: Ethynyl Influence and Y- and G-Dependences

Satoko Hayashi, Kentaro Yamane, Waro Nakanishi （Part： Lead author )

Bioinorganic Chemistry and Applications ( Hindawi Limited )  2009   1 - 11   2009  [Refereed]

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Fine structures of 8-G-1-(<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mi>p</mml:mi></mml:math>-<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:msub><mml:mtext>YC</mml:mtext><mml:mn>6</mml:mn></mml:msub><mml:msub><mml:mtext>H</mml:mtext><mml:mn>4</mml:mn></mml:msub><mml:mtext>C</mml:mtext><mml:mo> </mml:mo><mml:mo>≡</mml:mo><mml:mo> </mml:mo><mml:mtext>CSe</mml:mtext></mml:math>)<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:msub><mml:mtext>C</mml:mtext><mml:mrow><mml:mn>10</mml:mn></mml:mrow></mml:msub><mml:msub><mml:mtext>H</mml:mtext><mml:mn>6</mml:mn></mml:msub></mml:math>[<bold>1</bold>(G = H) and<bold>2</bold>(G = Cl): Y = H (<bold>a</bold>), OMe (<bold>b</bold>), Me (<bold>c</bold>), F (<bold>d</bold>), Cl (<bold>e</bold>), CN (<bold>f</bold>), and<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:msub><mml:mrow><mml:mtext>NO</mml:mtext></mml:mrow><mml:mn>2</mml:mn></mml:msub></mml:mrow></mml:math>(<bold>g</bold>)] are determined by the X-ray analysis. Structures of<bold>1</bold>,<bold>2</bold>, and<bold>3</bold>(G = Br) are called<bold>A</bold>if each Se–<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:msub><mml:mtext>C</mml:mtext><mml:mrow><mml:mtext>sp</mml:mtext></mml:mrow></mml:msub></mml:math>bond is perpendicular to the naphthyl plane, whereas they are<bold>B</bold>when the bond is placed on the plane. Structures are observed as<bold>A</bold>for<bold>1a</bold>–<bold>c</bold>bearing Y of nonacceptors, whereas they are<bold>B</bold>for<bold>1e</bold>–<bold>g</bold>with Y of strong acceptors. The change in the structures of<bold>1e</bold>–<bold>g</bold>versus those of<bold>1a</bold>–<bold>c</bold>is called Y-dependence in<bold>1</bold>. The Y-dependence is very specific in<bold>1</bold>relative to 1-(<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mi>p</mml:mi></mml:math>-<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:msub><mml:mtext>YC</mml:mtext><mml:mn>6</mml:mn></mml:msub><mml:msub><mml:mtext>H</mml:mtext><mml:mn>4</mml:mn></mml:msub></mml:math>Se)<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:msub><mml:mtext>C</mml:mtext><mml:mrow><mml:mn>10</mml:mn></mml:mrow></mml:msub><mml:msub><mml:mtext>H</mml:mtext><mml:mn>7</mml:mn></mml:msub></mml:math>(<bold>4</bold>) due to the ethynyl group: the Y-dependence in<bold>1</bold>is almost inverse to the case of<bold>4</bold>due to the ethynyl group. We call the specific effect “<italic>Ethynyl Influence.</italic>” Structures of<bold>2</bold>are observed as<bold>B</bold>: the<bold>A</bold>-type structure of<bold>1b</bold>changes dramatically to<bold>B</bold>of<bold>2b</bold>by G = Cl at the 8-position, which is called G-dependence. The structures of<bold>2</bold>and<bold>3</bold>are examined in solutions based on the NMR parameters.

DOI

Structures and dynamic stereochemistry of 9-arylselanyltriptycenes: X-ray crystallographic, spectroscopic and theoretical investigations

Takashi Nakamoto, Satoko Hayashi, Waro Nakanishi, Mao Minoura, Gaku Yamamoto

New Journal of Chemistry ( Royal Society of Chemistry (RSC) )  33 ( 7 ) 1588 - 1588   2009  [Refereed]

DOI

Imido transfer of sulfonylimino-λ3-bromane makes possible the synthesis of sulfonylimino-λ3-iodanes

Masahito Ochiai, Aiko Nakano, Akira Yoshimura, Kazunori Miyamoto, Satoko Hayashi, Waro Nakanishi

Chemical Communications ( Royal Society of Chemistry (RSC) )  ( 8 ) 959 - 959   2009  [Refereed]

DOI

How does non-covalent Se⋯SeO interaction stabilize selenoxides at naphthalene 1,8-positions: structural and theoretical investigations

Satoko Hayashi, Waro Nakanishi, Atsushi Furuta, Jozef Drabowicz, Takahiro Sasamori, Norihiro Tokitoh （Part： Lead author )

New J. Chem. ( Royal Society of Chemistry (RSC) )  33 ( 1 ) 196 - 206   2009  [Refereed]

DOI

Analysis of One-Bond Se-Se Nuclear Couplings in Diselenides and 1,2-Diselenoles on the Basis of Molecular Orbital Theory: Torsional Angular Dependence, Electron Density Influence, and Origin inJ1(Se, Se)

Akito Tanioku, Satoko Hayashi, Waro Nakanishi

Bioinorganic Chemistry and Applications ( Hindawi Limited )  2009   1 - 9   2009  [Refereed]

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Nuclear couplings for the Se-Se bonds,<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:mi>J</mml:mi><mml:mn>1</mml:mn><mml:mrow><mml:mo>(</mml:mo><mml:mrow><mml:mtext>Se, Se</mml:mtext></mml:mrow><mml:mo>)</mml:mo></mml:mrow></mml:mrow></mml:math>, are analyzed on the basis of the molecular orbital (MO) theory. The values are calculated by employing the triple<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mi>ζ</mml:mi></mml:math>basis sets of the Slater type at the DFT level.<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:mi>J</mml:mi><mml:mn>1</mml:mn><mml:mrow><mml:mo>(</mml:mo><mml:mrow><mml:mtext>Se, Se</mml:mtext></mml:mrow><mml:mo>)</mml:mo></mml:mrow></mml:mrow></mml:math>are calculated modeled by MeSeSeMe (<bold>1a</bold>), which shows the typical torsional angular dependence on<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:mi>ϕ</mml:mi><mml:mrow><mml:mo>(</mml:mo><mml:mrow><mml:msub><mml:mtext>C</mml:mtext><mml:mrow><mml:mtext>Me</mml:mtext></mml:mrow></mml:msub><mml:msub><mml:mrow><mml:mtext>SeSeC</mml:mtext></mml:mrow><mml:mrow><mml:mtext>Me</mml:mtext></mml:mrow></mml:msub></mml:mrow><mml:mo>)</mml:mo></mml:mrow></mml:mrow></mml:math>. The dependence explains well the observed<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:mi>J</mml:mi><mml:mn>1</mml:mn></mml:mrow></mml:math><mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:mrow><mml:mrow><mml:mo>(</mml:mo><mml:mrow><mml:mtext>Se, Se</mml:mtext></mml:mrow><mml:mo>)</mml:mo></mml:mrow></mml:mrow><mml:mrow><mml:mtext>obsd</mml:mtext></mml:mrow></mml:mrow></mml:math>of small values (<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:mo>≤</mml:mo><mml:mtext>64</mml:mtext></mml:mrow></mml:math> Hz) for<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:msup><mml:mtext>RSeSeR</mml:mtext><mml:mo>′</mml:mo></mml:msup></mml:math>(<bold>1</bold>) (simple derivatives of<bold>1a</bold>) and large values (330–380 Hz) observed for 4-substituted naphto[1,8-<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:mi>c</mml:mi><mml:mo>,</mml:mo><mml:mi>d</mml:mi></mml:mrow></mml:math>]-1,2-diselenoles (<bold>2</bold>) which correspond to<italic>symperiplanar</italic>diselenides.<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:mi>J</mml:mi><mml:mn>1</mml:mn></mml:mrow></mml:math>(Se, Se :<bold>2</bold>) becomes larger as the electron density on Se increases. The paramagnetic spin-orbit terms contribute predominantly. The contributions are evaluated separately from each MO<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:mrow><mml:mo>(</mml:mo><mml:mrow><mml:msub><mml:mi>ψ</mml:mi><mml:mi>i</mml:mi></mml:msub></mml:mrow><mml:mo>)</mml:mo></mml:mrow></mml:mrow></mml:math>and each<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:msub><mml:mi>ψ</mml:mi><mml:mi>i</mml:mi></mml:msub><mml:mo>→</mml:mo><mml:msub><mml:mi>ψ</mml:mi><mml:mi>a</mml:mi></mml:msub></mml:mrow></mml:math>transition, where<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:msub><mml:mi>ψ</mml:mi><mml:mi>i</mml:mi></mml:msub></mml:mrow></mml:math>and<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:msub><mml:mi>ψ</mml:mi><mml:mi>a</mml:mi></mml:msub></mml:mrow></mml:math>are occupied and unoccupied MO's, respectively. The separate evaluation enables us to recognize and visualize the origin and the mechanism of the couplings.

DOI

Atoms-in-molecules dual parameter analysis of weak to strong interactions: Behaviors of electronic energy densities versus Laplacian of electron densities at bond critical points

Waro Nakanishi, Satoko Hayashi, Kenji Narahara

Journal of Physical Chemistry A ( American Chemical Society (ACS) )  112 ( 51 ) 13593 - 13599   2008.12  [Refereed]

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AIM dual parameter analysis is proposed for the better understanding of weak to strong interactions: Total electron energy densities (H b(rc) are plotted versus Laplacian of electron densities (Δρb(rc)) at bond critical points (BCPs). Interactions examined in this work are those in van der Waals adducts, hydrogen bonded complexes, molecular complexes and hypervalent adducts through charge transfer (CT) interactions, and some classical covalent bonds. Data calculated at BCPs for the optimized distances (ro), together with ro - 0.1 Å, ro + 0.1 Å, and ro + 0,2 Å, are employed for the plots. The plots of Hb(rc) versus Δρb(rc) start from near origin (H b(rc) = Δρb(rc) = 0) and turn to the right drawing a helical stream as a whole. The helical nature is demonstrated to be controlled by the relative magnitudes of kinetic energy densities (Gb(rc)) and potential energy densities (V b(rc)), where Gb(rc) + V b(rc) = Hb(rc). Requirements for the data to appear in the specified quadrant are clarified. Points corresponding to the data will appear in the first quadrant (Δρb(r c) &gt
0 and Hb(rc) &gt
0) when -V b(rc) &lt
Gb(rc), they drop in the forth one (Δρb(rc) &gt
0 and H b(rc) &lt
0) if -(1/2)Vb(rc) &lt
Gb(rc) &lt
- Vb(rc), and they appear in the third quadrant (Δρb(rc) &lt
0 and Hb(rc) &lt
0) when Gb(rc) &lt
-(1/2)Vb(rc). No points will appear in the second quadrant (Δρb(rc) &lt
0 and Hb(r c) &gt
0). The physical meanings of the plots proposed in this work are also considered. The helical nature of the interactions in the plots helps us to understand the interactions in a unified way. © 2008 American Chemical Society.

DOI

Noncovalent Z···Z (Z=O, S, Se, and Te) Interactions: How Do They Operate to Control Fine Structures of 1,8-Dichalcogene-Substituted Naphthalenes?

Satoko Hayashi, Waro Nakanishi （Part： Lead author )

Bulletin of the Chemical Society of Japan ( The Chemical Society of Japan )  81 ( 12 ) 1605 - 1615   2008.12  [Refereed]

DOI

Fine structures of 8-G-1-(arylethynylselanyl)naphthalenes (G = H, Cl, Br): Factors to control the linear alignment of five G⋯Se-C{triple bond, long}C-CAr atoms in crystals and the behavior in solution

Kentaro Yamane, Satoko Hayashi, Waro Nakanishi, Takahiro Sasamori, Norihiro Tokitoh

Polyhedron ( Elsevier BV )  27 ( 18 ) 3557 - 3566   2008.12  [Refereed]

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8-G-1-(p-YC6H4C{triple bond, long}CSe)C10H6 [2 (G = Cl) and 3 (G = Br): Y = H (a), OMe (b), Me (c), F (d), Cl (e), CN (f) and NO2 (g)] have been prepared and the NMR spectra measured, in addition to 1 (G = H). Structures have been determined by X-ray crystallographic analysis for 2b, 2e and 2g, which are all type B (B), where the Se-Csp bond is placed in the naphthyl plane in B. The type is classified as A if the Se-Csp bond is perpendicular to the naphthyl plane. Structures around the p-YC6H4 (Ar) group are pd (perpendicular) for Y = OMe (2b) and Cl (2e) and pl (planar) for Y = NO2 (2g), where the Se-CNap bond is placed in the aryl plane in pl and perpendicular to the plane in pd. The 1b (A: pd) structure changes dramatically on going to 2b (B: pd) with G = Cl at the 8-position. The effect is called the G-dependence in 2. The G-dependence arises from the energy lowering effect of the np(Cl)⋯σ*(Se-Csp) 3c-4e interaction. Structures are both (B: pd) for 1e and 2e and both (B: pl) for 1g and 2g. One may realize that the structures are unchanged by G = Cl in place of G = H for Y = Cl and NO2 at a first glance. However, the B structures in 2e and 2g must be much more stabilized by the G-dependence of the np(Cl)⋯σ*(Se-Csp) 3c-4e interaction or the G⋯Se-Csp-Csp-Csp2 5c-6e type interaction. The structures of 2 and 3 are examined in solution based on the NMR parameters. The results show that 2 and 3 behave very similarly to each other and the structures are predominantly B, with some equilibrium between pd and pl around the aryl groups in solution. Quantum chemical calculations support the observations. © 2008 Elsevier Ltd. All rights reserved.

DOI

77Se NMR chemical shifts of 9-(arylselanyl)triprycenes: New standard for planar structures of ArSeR and applications to determine the structures in solutions

Takashi Nakamoto, Satoko Hayashi, Waro Nakanishi

Journal of Organic Chemistry ( American Chemical Society (ACS) )  73 ( 23 ) 9259 - 9269   2008.12  [Refereed]

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(Chemical Equation Presented) A set of new δ(Se) parameters is proposed as a standard for the planar (pl) orientational effect of p-YC 6H4 (Ar) in ArSeR, employing 9-(arylselanyl)triptycenes (1: p-YC6H4SeTpc). The Se-CR bond in ArSeR is placed on the Ar plane in pl and it is perpendicular to the plane in pd. Large upfield shifts are observed for Y = NMe2, OMe, and Me (-22 to -6 ppm) and large downfield shifts for Y = COOEt, CN, and NO2 (19-37 ppm), relative to Y = H, with small upfield and moderate downfield shifts by Y of halogens (-1 ppm for Y = F and 4 ppm for Y = Cl and Br). This must be the result of the p(Se)-π(C6H4)-p(Y) conjugation in 1 (pl). While the character of δ(Se) in 1 (pl) is very similar to that in 9-(arylselanyl)anthracenes (2 (pl)), it is very different from that of 1-(arylselanyl)anthraquinones (3 (pd)). Sets of δ(Se) of 1 and 2 must serve as the standard for pl and that of 3 does for pd in solutions. Structures of various ArSeR in solutions are determined from the viewpoint of the orientational effect based on the standard δ(Se) of 1-3. While the structure of 2-methyl-1-(arylselanyl)naphthalenes is concluded to be all pl in solutions, those of 8-chloro- and 8-bromo-1-(arylselanyl)naphthalenes are all pd, except for Y = COOEt, CN, and NO2: The equilibrium between pd and pl contributes to those with Y = COOEt, CN, and NO2. The structure of 1-(arylselanyl)naphthalenes changes depending on Y. The structures of ArSeMe and ArSeCOPh are shown to be pl and pd, respectively, in solutions. Those of ArSePh and ArSeAr seem to change depending on Y. δ(Se) of 1-3 are demonstrated to serve as the standard to determine the structures in solutions. The rules of thumb derived from the characters in δ(Se) for 1-3 are very useful to determine the structures of ArSeR in solutions, in addition to the analysis based on the plots. © 2008 American Chemical Society.

DOI

Contributions from Atomic p(Se), d(Se), and f(Se) Orbitals to Absolute Paramagnetic Shielding Tensors in Neutral and Charged SeHnand Some Oxides Including the Effect of Methyl and Halogen Substitutions on σp(Se)

Waro Nakanishi, Satoko Hayashi, Kenji Narahara, Masahiko Hada

Chemistry - A European Journal ( Wiley )  14 ( 31 ) 9647 - 9655   2008.10  [Refereed]

DOI

Evaluation of electron population terms for (rSe -3)4p, (rS-3)3p, and (rO-3)2p: How do HOMO and LUMO shrink or expand depending on nuclear charges?

Waro Nakanishi, Satoko Hayashi, Kenji Narahara, Daisuke Yamaki, Masahiko Hada

Chemistry - A European Journal ( Wiley )  14 ( 24 ) 7278 - 7284   2008.08  [Refereed]

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Electron population terms (rN-3) are evaluated for N = Se, S, and O. Calculations are performed on HOMO and LUMO constructed by pure atomic 4p(Se), 3p(S), and 2p(O) orbitais, employing the 6-311+G(3d) and/or 6-311 ++G(3df,3pd) basis sets at the HF, MP2, and DFT (B3LYP) levels. Se 4+, Se2+, Se0, and Se2- with the Oh symmetry are called G(A: Se) and HSe+, H2Se, and HSe- with the C∞h or C2v symmetry are named G(B: Se), here [G(A+B: Se) in all]. HOMO and LUMO in G(A+B: N) (N=Se, S, and O) satisfy the conditions of the calculations for (rN -3). The (rSe-3)4p, (r S-3)3p, and (rO-3) 2p values correlate well with the corresponding MO energies (εN) for all calculation levels employed. Plots of (r N-3)HOMO and (rN-3) LUMO versus Q(N) (N=Se, S, and O) at the HF and MP2 levels are analyzed as two correlations. However, the plots at the DFT level can be analyzed as single correlation. A regression curve is assumed for the analysis. Behaviors of (rN-3) clarify how valence orbitals shrink or expand depending on Q(N). The applicability of (rN-3) is examined to establish a new method that enables us to analyze chemical shifts with the charge effect separately from others. A utility program derived from the Gaussian 03 (NMRANAL-NH03G) is applied to evaluate (rN -3) and examine the applicability to the NMR analysis. © 2008 Wiley-VCH Verlag GmbH &amp
Co. KGaA,.

DOI

Fine structures of 1-(arylethynylselanyl)naphthalenes: Characteristic features brought by the ethynylselanyl group

Kentaro Yamane, Satoko Hayashi, Waro Nakanishi, Takahiro Sasamori, Norihiro Tokitoh

Polyhedron ( Elsevier BV )  27 ( 11 ) 2478 - 2486   2008.08  [Refereed]

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Fine structures of 1-(arylethynylselanyl)naphthalenes [1-(p-YC6H4C{triple bond, long}CSe)C10H7: 1, Y = H (a), OMe (b), Me (c), Cl (e), CN (h), NO2 (i)] have been determined by X-ray crystallographic analysis. The structures are A for 1a-c, bearing Y that is a non-acceptor, B for 1e, 1h and 1i, having Y that is a strong acceptor, where the Se-Csp bond is perpendicular to the naphthyl plane in A, but is in the plane in B
and C is intermediate between A and B (see Scheme 1). The Y-dependence observed in 1 is just the opposite to the case of 1-(arylselanyl)naphthalenes [1-(p-YC6H4Se)C10H7]. We call the factor the "ethynyl effect", which controls the fine structures of 1. The structures of 1h and 1i are planar or almost planar. The energy lowering effect by the parallel direction between np(Se) and np(Y) must be responsible for the observations if Y is a strong acceptor. The origin of the ethynyl effect is explained by how effectively np(Se) and np(Y) interact through the C{triple bond, long}C bond. Crystal packing effects, such as the formation of dimmers, also play an important role in determining the fine structures of 1. The dimer formation in 1a-c substantially stabilizes the structures. The π-stacking of naphthyl groups may also contribute to the dimer formation. The structures in solutions are also clarified. Compound 1 exist in the A form in solutions, with some equilibration with B. The ethynyl effect as the factor that controls the fine structures of 1 is also confirmed in solution. The results are well supported by quantum chemical calculations on the structures, energy profiles and the evaluation of electron affinity. The NMR chemical shifts explain the behavior of 1 in solution. © 2008 Elsevier Ltd. All rights reserved.

DOI

Torsional angular dependence of1J(Se,Se) and fermi contact control of4J(Se,Se): Analysis ofnJ(Se,Se) (n = 1-4) based on molecular orbital theory

Waro Nakanishi, Satoko Hayashi

Chemistry - A European Journal ( Wiley )  14 ( 18 ) 5645 - 5655   2008.06  [Refereed]

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nJ(Se,Se) (n = 1-4) nuclear couplings between Se atoms were analyzed by using molecular orbital (MO) theory as the first step to investigating the nature of bonded and nonbonded nJ(Se,Se) interactions between Se atoms. The values were calculated by employing Slater-type triple ξ basis sets at the DFT level, which were applied to structures optimized with the Gaussian 03 program. The contribution from each occupied MO (Ψi) and Ψi-Ψa (Ψa = unoccupied MO) transition was evaluated separately. 1J(Se,Se) was calculated for the MeSeSeMe model compound, which showed a typical dependence on the torsion angle (φ(CMeSeSeC Me)). This dependence explains the small values (≤64Hz) of 1Jobsd(Se,Se) observed for RSeSeR′ and large values (330-380 Hz) of 1Jobse- (Se,Se) observed for 4-substituted naphtho[1,8-c,d]-1,2-diselenoles, which correspond to synperiplanar diselenides. The HOMO-+LUMO and HOMO-1 → LUMO transitions contribute the most to 1J(Se,Se) at φ = 0 and 180° to give large values of 1J-(Se,Se), whereas various transitions contribute and cancel each other out at φ = 90° to give small values of 1J-(Se,Se). Large 4Jobsd(Se,Se) values were also observed in the nonbonded Se⋯Se, Se⋯Se=O, and O=Se⋯Se=O interactions at naphthalene 1,8-positions. The Fermi contact (FC) term contributes significantly to 4J(Se,Se), whereas the paramagnetic spin-orbit (PSO) term contributes significantly to 1J-(Se,Se). 2J(Se,Se) and 3J(Se,Se) were analyzed in a similar manner and a torsional angular dependence was confirmed for 3J(Se,Se). Depending on the structure, the main contribution to nJ-(Se,Se) (H = 2, 3) is from the FC term, with a lesser contribution from the PSO term. Analysis of each transition enabled us to identify and clearly visualize the origin and mechanism of the couplings. © 2008 Wiley-VCH Verlag GmbH &amp
Co. KGaA.

DOI

Origin of 77Se NMR Chemical Shifts Revealed for Pre-α, α, β, and γ Effects

Satoko Hayashi, Waro Nakanishi （Part： Lead author )

Phosphorus, Sulfur, and Silicon and the Related Elements ( Informa UK Limited )  183 ( 4 ) 1067 - 1071   2008.04  [Refereed]

DOI

X-ray characterization of Te(S2CNC5H10)2 and TeI2[(C13H10N2S)2] · 4C4H8TeI2; the first Te-C bond cleaved products obtained in the substitution reactions of organo(heterocyclic)tellurium(IV) derivatives

Prakash C. Srivastava, Sangeeta Bajpai, Roli Lath, Rajesh Kumar, Vikas Singh, Shrinkhala Dwivedi, Ray J. Butcher, Satoko Hayashi, Waro Nakanishi

Polyhedron ( Elsevier BV )  27 ( 2 ) 835 - 848   2008.02  [Refereed]

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The reaction of organo(heterocyclic)tellurium(IV) derivative: C8H8TeI2(1,3-dihydro-2λ4-benzotellurole-2,2-diyl diiodide) with NH4S2CNC5H10 (ammonium piperidine dithiocarbamate) gives C8H8Te(S2CNC5H10)2 (1) and Te(S2CNC5H10)2 (2) or C8H8TeI(S2CNC5H10) (5) according to the reaction conditions. In such type of metathetical reactions, the formation of 2 is unprecedented and it corresponds to the first Te-C cleaved product. The reaction of 2 with CH3I, yields the oxidative addition product, CH3TeI(S2CNC5H10)2 (8). The formation of 2 is also supported through Quantum Chemical calculations. Another Te-C bond cleaved product TeI2[(C13H10N2S)2] · 4C4H8TeI2 (9) is obtained in the reaction of C4H8TeI2 (1,1,2,3,4,5-hexahydro-1,1-diiodotellurophene) with NH4S2CNHC6H5 (ammonium aniline dithiocarbamate). The reaction of 1,1,2,3,4,5,6-heptahydro-1-iodo-1-(morpholine dithiocarbamato) tellurane [C5H10TeI(S2CNC4H8O)] (10) with 1,10-phenanthroline gives an unusual product C12H8N2 · C4H10INO (11). The structures of the new complexes 2, 8, 9, 10 and 11 have been determined by the X-ray analysis. © 2008 Elsevier Ltd. All rights reserved.

DOI

Extended hypervalent E′⋯E–E⋯E′ 4c–6e (E, E′ = Se, S) interactions: structure, stability and reactivity of 1-(8-PhE′C10H6)EE(C10H6E′Ph-8′)-1′

Waro Nakanishi, Satoko Hayashi, Sayuri Morinaka, Takahiro Sasamori, Norihiro Tokitoh

New Journal of Chemistry ( Royal Society of Chemistry (RSC) )  32 ( 11 ) 1881 - 1881   2008  [Refereed]

DOI

A new type of imido group donor: Synthesis and characterization of sulfonylimino-Δ3-bromane that acts as a nitrenoid in the aziridination of olefins at room temperature under metal-free conditions

Masahito Ochiai, Takao Kaneaki, Norihiro Tada, Kazunori Miyamoto, Hiroshi Chuman, Motoo Shiro, Satoko Hayashi, Waro Nakanishi

Journal of the American Chemical Society ( American Chemical Society (ACS) )  129 ( 43 ) 12938 - 12939   2007.10  [Refereed]

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A stable sulfonylimino-λ3-bromane, CF3SO2N--Br+C6H4-p-CF3, has been synthesized and structurally characterized for the first time. X-ray crystallographic analyses indicated a centrosymmetric dimer structure with little double-bond character for the "ylidic" Br-N bond. The iminobromane serves as an efficient imido group donor and directly undergoes aziridination of olefins stereospecifically with retention of original stereochemistry. Very interestingly, the aziridination proceeds at room temperature using limiting amounts of alkenes under transition-metal-free conditions. The observed rate constants for aziridination of cis-cyclooctene are proportional to concentration of the olefin. The results suggest the involvement of a bimolecular transition state, in which an olefin attacks the σ* N-Br orbital of iminobromane in the nitrenoid transfer process. Copyright © 2007 American Chemical Society.

DOI

Orientational effect of aryl groups in aryl selenides: How can 1H and 13C NMR chemical shifts clarify the effect?

Satoko Hayashi, Kentaro Yamane, Waro Nakanishi （Part： Lead author )

Journal of Organic Chemistry ( American Chemical Society (ACS) )  72 ( 20 ) 7587 - 7596   2007.09  [Refereed]

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(Chemical Equation Presented) Two sets of δ(H) and δ(C) are proposed by employing 9-(arylselanyl)anthracenes [9-(p-YC6H 4Se)Atc: 1] and 1-(arylselanyl)anthraquinones [1-(p-YC 6H4Se)Atq: 2] with various Y's. Structures of 1 and 2 are (A: pl) and (B: pd), respectively, for all Y examined in chloroform-d. After elucidation of the behavior of δ(H, C: 1) and δ(H, C: 2), they are applied to determine the structures in chloroform-d solutions for 1-(arylselanyl)naphthalenes (3), 1-(arylselanyl)-2-methylnaphthalenes (4), and 1-(arylselanyl)-8-bromonaphthalenes (5). Although the structure of 4 remains in (A: pl) in the solutions for all Y examined, that of 5 is (B: pd), except for Y = CN and NO2. On the other hand, 3 is shown to equilibrate between (A: pl) and (B: pd). Although the contributions of (B: pd) and (A: pl) are predominant for Y = NMe2 and NO2, respectively, the equilibrium constants change from Y to Y in the solutions. The results are supported by the quantum chemical calculations, containing the solvent effect of chloroform. These results demonstrate that δ(H, C: 1) and δ(H, C: 2), as well as δ(Se), serve as the practical standards for pl and pd, respectively, to analyze the structures of p-YC6H4ZR (Z = Se) in solutions. © 2007 American Chemical Society.

DOI

How 77Se NMR Chemical Shifts Originate from Pre-α, α, β, and γ Effects: Interpretation Based on Molecular Orbital Theory

Waro Nakanishi, Satoko Hayashi, Masahiko Hada

Chemistry - A European Journal ( Wiley )  13 ( 18 ) 5282 - 5293   2007.06  [Refereed]

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Plain rules founded in a theoretical background are presented that, can be used to determine the structure of selenium compounds on the basis of 6(Se) data and to predict (5(Se) data from a given structure with satisfactory accuracy. As a first step to establish such rules, the origin of 6(Se) is elucidated on the basis of MO theory. The Se2- ion was chosen as the standard for the analysis. The concept of the pre-alpha effect is proposed, which is defined as the downfield shift due to protonation of a lone-pair orbital of Se. The pre-a effect of two protons in H,Se is explained by the generation of double sigma(Se-H) and sigma*(Se-H) through protonation of the spherical Se2- ion. The orbitals, together with n(p)(Se), result in effective transitions for the pre-alpha effect. The a effect is the downfield shift caused by the replacement of Se-H by Se-Me. The extension of HOMO-2 [4p(y)(Se)], HOMO-1 [4p(x)(Se)], and HOMO [4p(z)(Se)] over the whole Me,Se molecule is mainly responsible for the alpha effect. The beta effect originates not from the occupied-to-unoccupied (psi(i)-&gt;psi(a)) transitions but from the occupied-to-occupied (psi(i)-&gt;psi(j)) transitions. Although psi(i)-&gt;psi(j) transitions contribute to upfield shifts in Me2Se, the magnitudes become smaller as the methyl protons are substituted by Me groups one after another. The gamma effect of upfield shifts is also analyzed, although complex. The effect of p(Se)-pi(C=C) conjugation is analyzed in relation to the orientational effect. Contributions from each MO (psi(i)) and each psi(i)-&gt;psi(a) transition are evaluated separately, by using a utility program derived from the Gaussian 03 program suite (NMRANAL.-NH03G). The treatment enables us to visualize and understand the origin of Se-77 NMR chemical shifts.

DOI

Structures in 8-(methylselanyl)-1-(methylseleninyl)- and 1,8-bis(methylseleninyl)naphthalenes: Transition states involving simultaneous rotation around Se{single bond}C bonds, together with stable structures

Satoko Hayashi, Waro Nakanishi （Part： Lead author )

Journal of Molecular Structure: THEOCHEM ( Elsevier BV )  811 ( 1-3 ) 293 - 301   2007.06  [Refereed]

　View Summary

The energy profile of 8-(methylselanyl)-1-(methylseleninyl)naphthalene (1) is revealed to clarify how the Se(O)Me and SeMe groups control the stereochemistry of 1, through the nonbonded Se-Se{double bond, long}O interaction. Six stable structures (SSs) and eight transition states (TSs) are optimized for 1. Frequency analysis is carried out for all SSs and TSs. The global minimum of 1 is the trans-form of 1 (1 (t-AA)), which reproduces the structure determined by the X-ray crystallographic analysis. Three Se-Se{double bond, long}O atoms in 1 (t-AA) are on the naphthyl plane and two Me groups are in trans. Next stable one is the cis-form (1 (c-AC′)). Motions in the imaginary frequencies of six TSs correspond to the rotation around an Se{single bond}CNap bond, whereas those of the two to the simultaneous rotations around the two Se{single bond}CNap bonds. Attractive interactions must play an important but additional role in the simultaneous rotations in TS. The observed structure in 1,8-bis(methylseleninyl)naphthalene (2) is also reproduced by the global minimum, where the four O{double bond, long}Se-Se{double bond, long}O atoms align linearly. NBO analysis reveals that σ(3c-4e) of the nonbonded Se-Se{double bond, long}O interaction controls the structure of 1 whereas σ(4c-4e) of the O{double bond, long}Se-Se{double bond, long}O interaction will not in 2. © 2007 Elsevier B.V. All rights reserved.

DOI

Atoms-in-molecules analysis of extended hypervalent five-center, six-electron (5c-6e) C2Z2O interactions at the 1,8,9-positions of anthraquinone and 9-methoxyanthracene systems

Waro Nakanishi, Takashi Nakamoto, Satoko Hayashi, Takahiro Sasamori, Norihiro Tokitoh

Chemistry - A European Journal ( Wiley )  13 ( 1 ) 255 - 268   2007  [Refereed]

　View Summary

To clarify the nature of five-center, six-electron (5c-6e) C 2Z2O interactions, atoms-in-molecules (AIM) analysis has been applied to an anthraquinone, 1,8-(MeZ)2ATQ (1 (Z = Se), 2 (Z = S), and 3 (Z = O)), and a 9-methoxyanthracene system, 9-MeO-1,8-(MeZ) 2ATC (4 (Z = Se), 5 (Z = S), and 6 (Z = O)), as well as 1-(MeZ)ATQ (7 (Z = Se), 8 (Z = S), and 9 (Z = O)) and 9-MeO-1-(MeZ)ATC (10 (Z = Se), 11 (Z = S), and 12 (Z = O)). The total electronic energy density (Hb(r c)) at the bond critical points (BCPs), an appropriate index for weak interactions, has been examined for 5c-6e C2Z2O and 3c-4e CZO interactions of the np(O)⋯σ*(Z-C) type in 1-12. Some hydrogen-bonded adducts were also re-examined for convenience of comparison. The total electronic energy densities varied in the following order: O⋯O (3: Hb(rc) = 0.0028 au) = O⋯O (6: 0.0028 au) &gt
O⋯O (9: 0.0025 au) ≥ NN⋯HF (0.0024 au) ≥ O⋯O (12: 0.0023 au) ≫ H2O⋯HOH (0.0015 au) &gt
S⋯O (8: 0.0013 au) = S⋯O (2: 0.0013 au) &gt
S⋯O (11: 0.0012 au) = S⋯O (5: 0.0012 au) &gt
HF⋯HF (0.0008 au) = Se⋯O (10: 0.0008 au) = Se⋯O (4: 0.0008 au) ≥ Se⋯O (1: 0.0007 au) ≥ Se⋯O (7: 0.0006 au) ≫ HCN⋯HF (-0.0013 au). Hb(rc) values for S⋯O were predicted to be smaller than the hydrogen bond of H2O⋯HOH and Hb(r c) values for Se⋯O are very close to or slightly smaller than that for HF⋯HF in both the ATQ and 9-MeOATC systems. In the case of Z = Se and S, Hb(rc) values for 5c-6e C2Z 2O interactions are essentially equal to those for 3c-4e CZO if Z is the same. The results demonstrate that two np(O) ⋯σ*(Z-C) 3c-4e interactions effectively connect through the central np(O) orbital to form the extended hypervalent 5c-6e system of the σ*(C-Z)-np(O)⋯σ* (Z-C) type for Z = Se and S in both systems. Natural bond orbital (NBO) analysis revealed that ns(O) also contributes to some extent. The electron charge densities at the BCPs, NBO analysis, and the total energies calculated for 1-12, together with the structural changes in the PhSe derivatives, support the above discussion. © 2007 Wiley-VCH Verlag GmbH &amp
Co. KGaA.

DOI

Structures of 1-(arylseleninyl)naphthalenes: O, G, and Y dependences in 8-G-1-[p-YC6H4Se(O)]C10H6

Satoko Hayashi, Hideki Wada, Takashi Ueno, Waro Nakanishi （Part： Lead author )

Journal of Organic Chemistry ( American Chemical Society (ACS) )  71 ( 15 ) 5574 - 5585   2006.07  [Refereed]

　View Summary

Structures of 8-G-1-[p-YC6H4Se(O)]C 10H6 [1 (G = H), 2 (G = F), 3 (G = Cl), and 4 (G = Br): Y = H, OMe, OCH2Ph, t-Bu, Me, Cl, and NO2] and (1-C 10H7)2SeO (5) are investigated by the X-ray crystallographic analysis. Structures of 1 are all A with regard to the naphthyl group (1 (A)), where the Se-CAr and Se-O bonds are perpendicular to and parallel to the naphthyl plane, respectively. Those of 2-4 are also A. Since structures of 8-G-1-(p-YC6H4Se)C10H 6 [7 (G = F), 8 (G = Cl), and 9 (G = Br)] are all B, the results exhibit that B of 7-9 change dramatically to A of 2-4 with the introduction of O atoms. The factor to determine the A structures of 1-4 by O is called O dependence. The origin of the O dependence is the nonbonded np(O)- - -π(Nap) interaction, which results in CT from np(O) to π(Nap) since O in 1-4 is highly electron rich due to the polar Se+=O - bond and π(Nap) acts as an acceptor. There are two types of np(O)'s, npy(O) and npz(O), if the directions of the Se-O bond and the p-orbitals of π(Nap) are taken in the x- and z-axes, respectively. Double but independent np(O)- - -π(Nap) interactions in 5 lead to 5 (AA). The conformation of the p-YC6H 4Se group in 1 changes depending on Y (Y dependence), although the effect is not strong. The Y dependence is explained on the basis of the magnitude of CT of the np(O)→π(Ar) type in 1, in addition to the np(O)- - -σπ(Nap) interaction. The structure around the Se=O group in 1 is close to that of 5 (AA), if the accepting ability of the p-YC6H4Se group is similar to that of the naphthyl group. A of 2-4 are further stabilized by the np(G)- - -σ*(Se-O) 3c-4e interactions, which are called G dependence. QC calculations performed on the methyl analogues of 1-4 (11-14, respectively) reproduced the observed structures, supported the above discussion, and revealed the energy profiles. The energy-lowering effect of the O dependence would be close to the G dependence of the nonbonded n(Br)- - -σ*(Se-O) 3c-4e interaction in 14 if the steric repulsion between Br and Se is contained in the G dependence. The value is roughly predicted as 20 kJ mol-1. The structures of 1-5 are well explained by O, G, and Y dependences. © 2006 American Chemical Society.

DOI

Orientational Effect of Aryl Groups on77Se NMR Chemical Shifts: Experimental and Theoretical Investigations

Waro Nakanishi, Satoko Hayashi, Daisuke Shimizu, Masahiko Hada

Chemistry - A European Journal ( Wiley )  12 ( 14 ) 3829 - 3846   2006.05  [Refereed]

DOI

Proposal for Sets of77Se NMR Chemical Shifts in Planar and Perpendicular Orientations of Aryl Group and the Applications

Satoko Hayashi, Waro Nakanishi （Part： Lead author )

Bioinorganic Chemistry and Applications ( Hindawi Limited )  2006   1 - 13   2006  [Refereed]

　View Summary

The orientational effect of<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" id="E1"><mml:mrow><mml:mi>p</mml:mi><mml:mtext>-</mml:mtext><mml:msub><mml:mrow><mml:mtext>YC</mml:mtext></mml:mrow><mml:mn>6</mml:mn></mml:msub><mml:msub><mml:mtext>H</mml:mtext><mml:mn>4</mml:mn></mml:msub></mml:mrow></mml:math>(Ar) on<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" id="E2"><mml:mi>δ</mml:mi></mml:math>(Se) is elucidated for ArSeR, based on experimental and theoretical investigations. Sets of<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" id="E3"><mml:mi>δ</mml:mi></mml:math>(Se) are proposed for<bold>pl</bold>and<bold>pd</bold>employing 9-(arylselanyl)anthracenes (<bold>1</bold>) and 1-(arylselanyl)anthraquinones (<bold>2</bold>), respectively, where Se–<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" id="E4"><mml:mrow><mml:msub><mml:mi>C</mml:mi><mml:mi>R</mml:mi></mml:msub></mml:mrow></mml:math>in ArSeR is on the Ar plane in<bold>pl</bold>and perpendicular to the plane in<bold>pd</bold>. Absolute magnetic shielding tensors of Se (<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" id="E5"><mml:mi>σ</mml:mi></mml:math>(Se)) are calculated for ArSeR (R = H, Me, and Ph), assuming<bold>pl</bold>and<bold>pd</bold>, with the DFT-GIAO method. Observed characters are well reproduced by the total shielding tensors (<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" id="E6"><mml:mrow><mml:msup><mml:mi>σ</mml:mi><mml:mtext>t</mml:mtext></mml:msup></mml:mrow></mml:math>(Se)). The paramagnetic terms (<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" id="E7"><mml:mrow><mml:msup><mml:mi>σ</mml:mi><mml:mtext>P</mml:mtext></mml:msup></mml:mrow></mml:math>(Se)) are governed by<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" id="E8"><mml:mrow><mml:msup><mml:mi>σ</mml:mi><mml:mtext>P</mml:mtext></mml:msup><mml:msub><mml:mrow><mml:mo>(</mml:mo><mml:mtext>Se</mml:mtext><mml:mo>)</mml:mo></mml:mrow><mml:mrow><mml:mtext>xx</mml:mtext></mml:mrow></mml:msub><mml:mo>+</mml:mo><mml:msup><mml:mi>σ</mml:mi><mml:mtext>P</mml:mtext></mml:msup><mml:msub><mml:mrow><mml:mo>(</mml:mo><mml:mtext>Se</mml:mtext><mml:mo>)</mml:mo></mml:mrow><mml:mrow><mml:mtext>yy</mml:mtext></mml:mrow></mml:msub></mml:mrow></mml:math>, where the direction of<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" id="E9"><mml:mrow><mml:msub><mml:mtext>n</mml:mtext><mml:mtext>P</mml:mtext></mml:msub></mml:mrow></mml:math>(Se) is set to the<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" id="E10"><mml:mi>z</mml:mi></mml:math>-axis. The mechanisms of the orientational effect are established both for<bold>pl</bold>and<bold>pd</bold>. Sets of<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" id="E11"><mml:mi>δ</mml:mi></mml:math>(Se:<bold>1</bold>) and<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" id="E12"><mml:mi>δ</mml:mi></mml:math>(Se:<bold>2</bold>) act as the standards for<bold>pl</bold>and<bold>pd</bold>, respectively, when<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" id="E13"><mml:mi>δ</mml:mi></mml:math>(Se) of ArSeR are analyzed based on the orientational effect.

DOI

The Structure of 1-(Arylthio)naphthalenes, Together with the Selenium and Oxygen Derivatives in Crystals and Solutions

Waroˆ Nakanishi, Satoko Hayashi, Takahito Nakai

Phosphorus, Sulfur, and Silicon and the Related Elements ( Informa UK Limited )  180 ( 5-6 ) 1431 - 1432   2005.03  [Refereed]

DOI

Extended Hypervalent 5c–6e Interactions: Linear Alignment of Five C─Z- - -O- - -Z─C (Z = S, Se) Atoms in Anthraquinone and Anthracene Systems

Warô Nakanishi, Satoko Hayashi, Takashi Furuta, Norio Itoh, Yusaku Nishina, Makoto Yamashita, Yohsuke Yamamoto

Phosphorus, Sulfur, and Silicon and the Related Elements ( Informa UK Limited )  180 ( 5-6 ) 1351 - 1355   2005.03  [Refereed]

DOI

How Do G–Se Nonbonded and Y–Se Through π -Bond Interactions Determine the Structures of 8-G-1-( p-YC6H4Se)C10H6?

Warô Nakanishi, Satoko Hayashi

Phosphorus, Sulfur, and Silicon and the Related Elements ( Informa UK Limited )  180 ( 3-4 ) 961 - 964   2005.02  [Refereed]

DOI

Extend Hypervalent 5c-6e Interactions: Linear Alignment of Five C-Se- - -O- - -Se-C Atoms in Anthraquinone and 9-Methoxyanthracene Bearing Arylselanyl Groups at the 1,8-Positions

Warô Nakanishi, Satoko Hayashi, Norio Itoh

Journal of Organic Chemistry ( American Chemical Society (ACS) )  69 ( 5 ) 1676 - 1684   2004.03  [Refereed]

　View Summary

The structures of 1,8-bis(phenylselanyl)anthraquinone (1a), 1,8-bis(phenylselanyl)-9-methoxyan-thracene (2a), and 1,8-bis(phenylselanyl)anthracene (3a) are determined by X-ray crystallographic analysis, together with the derivatives. The Se-Ci (Ph) bonds in 1a are placed on the anthraquinone plane (both type B) and the phenyl planes are perpendicular to the anthraquinone plane. The structure around the Se atoms in 2a is very close to that of 1a: the conformations of the PhSe groups are both type B. Consequently, the five Ci-Se- - -O- - -Se-Ci atoms in 1a and 2a align linearly. The nonbonded Se- - -O distances in 1a and 2a are 2.673-2.688 and 2.731-2.744 Å, respectively, which are about 0.7 Å shorter than the sum of van der Waals radii of the atoms. The extended hypervalent σ*(Ci-Se)- - -np(O)- - -σ*(Se-Ci) 5c-6e interactions are strongly suggested for the origin of the linear alignment of the five atoms in 1a and 2a. The 5c-6e must be constructed by the connection of the two hypervalent np(O)- - -σ*(Se-Ci) 3c-4e interactions through the central n p(O). The five Ci-Se- - -H- - -Se-Ci atoms never align linearly in 3a. To reveal the nature of 5c-6e in 1a and 2a, QC calculations are performed on HaHbASe- - -O(=CH2)- - -BSeHa′Hb′ (model a) and HaHbASe- - -OH2- - -BSeHa′Hb′ (model b) with the B3LYP/6-311++G(3df,2pd) method, where the nonbonded Se- - -O distances are fixed at 2.658 Å. Four conformers, a (AA-cis), a (AA-trans), a (AB), and a (BB), are optimized to be stable for model a, where a (AA) shows both type A for the ASe-Hb and BSe-Hb′ bonds in model a. Three conformers, b (AA-cis), b (AB), and b (BB), are stable for model b. The bonding models in AA, AB, and BB correspond to 3c-6e, 4c-6e, and 5c-6e, respectively. The models become more stable by 42 ± 5 kJ mol-1, if the type A conformation of each Se-H bond changes to type B. No noticeable saturation is observed in the stabilization for each change. QC calculations are also performed on 1a-3a at the B3LYP level. Three conformers are evaluated to be stable for 1a and 2a. The relative energies of 1a (AA-trans), 1a (AB), and 1a (BB) are 0.0, -31.5, and -60.6 kJ mol -1, respectively, and those of 2a (AA-cis), 2a (AB), and 2a (BB) are 0.0, -24.4, and -36.5 kJ mol-1, respectively. These results demonstrate that the origin of the linear alignment of the five C-Se- - -O- - -Se-C atoms in 1a and 2a is the energy lowering effect by the extended hypervalent 5c-6e interactions of the σ*(C-Se)←n p(O)→σ*(Se-C) type. The π-conjugation between π(C=O) and npz(Se) through the π-framework of anthraquinone must also contribute to stabilize the BB structure of 1a, where z is the direction perpendicular to the anthraquinone plane.

DOI

First Br4four centre–six electron and Se2Br5seven centre–ten electron bonds in nonionic bromine adducts of selenanthrene

Warô Nakanishi, Satoko Hayashi, Shigehiro Yamaguchi, Kohei Tamao

Chem. Commun. ( Royal Society of Chemistry (RSC) )  ( 2 ) 140 - 141   2004  [Refereed]

DOI

First linear alignment of five C–Se⋯O⋯Se–C atoms in anthraquinone and 9-(methoxy)anthracene bearing phenylselanyl groups at 1,8-positions

Warô Nakanishi, Satoko Hayashi, Norio Itoh

Chem. Commun. ( Royal Society of Chemistry (RSC) )  ( 1 ) 124 - 125   2003  [Refereed]

DOI

Linear alignment of four sulfur atoms in bis[(8-phenylthio)naphthyl] disulfide: contribution of linear S4 hypervalent four-centre six-electron bond to the structure

War?? Nakanishi, Satoko Hayashi, Takamitsu Arai

Chemical Communications ( Royal Society of Chemistry (RSC) )  ( 20 ) 2416 - 2417   2002.10  [Refereed]

DOI

Nonbonded P···P and P···Se Interactions in Naphthalene 1,8-Positions: Role of Lone-Pair Orbitals

Warô Nakanishi, Satoko Hayashi

Phosphorus, Sulfur, and Silicon and the Related Elements ( Informa UK Limited )  177 ( 6-7 ) 1833 - 1837   2002.06  [Refereed]

DOI

Structural studies on diaryl selenide dihalides in solution: molecular complex formation of substituted diphenyl selenides with bromine

Warô Nakanishi, Satoko Hayashi, Yoshiaki Kusuyama

Journal of the Chemical Society, Perkin Transactions 2 ( Royal Society of Chemistry (RSC) )  ( 2 ) 262 - 270   2002.01  [Refereed]

DOI

Structure of 1-(Arylselanyl)naphthalenes. 2. G Dependence in 8-G-1-(p-YC6H4Se)C10H6

Warô Nakanishi, Satoko Hayashi

The Journal of Organic Chemistry ( American Chemical Society (ACS) )  67 ( 1 ) 38 - 48   2002.01  [Refereed]

DOI

Structure of 1-(Arylselanyl)naphthalenes − Y Dependence in 1-(p-YC6H4Se)C10H7

Warô Nakanishi, Satoko Hayashi, Tetsutaro Uehara

European Journal of Organic Chemistry ( Wiley )  2001 ( 20 ) 3933 - 3943   2001.10  [Refereed]

DOI

On the equilibrium between molecular complexes and trigonal bipyramidal adducts of diaryl selenide dibromides in solution

War? Nakanishi, Satoko Hayashi

Heteroatom Chemistry ( Wiley )  12 ( 5 ) 369 - 379   2001  [Refereed]

DOI

Inter-element linkage in 1,2- and 1,4-bis(arylselanyl)benzenes with halogens

Warô Nakanishi, Satoko Hayashi

Journal of Organometallic Chemistry ( Elsevier BV )  611 ( 1-2 ) 178 - 189   2000.10  [Refereed]

DOI

Successive Change in Conformation Caused byp-Y Groups in 1-(MeSe)-8-(p-YC6H4Se)C10H6:  Role of Linear Se···Se−C Three-Center−Four-Electron versus n(Se)···n(Se) Two-Center−Four-Electron Nonbonded Interactions

Warô Nakanishi, Satoko Hayashi, Tetsutaro Uehara

The Journal of Physical Chemistry A ( American Chemical Society (ACS) )  103 ( 48 ) 9906 - 9912   1999.12  [Refereed]

DOI

Novel Substituent Effect on77Se NMR Chemical Shifts Caused by 4c-6e versus 2c-4e and 3c-4e in Naphthalene Peri Positions:  Spectroscopic and Theoretical Study

Satoko Hayashi, Warô Nakanishi （Part： Lead author )

The Journal of Organic Chemistry ( American Chemical Society (ACS) )  64 ( 18 ) 6688 - 6696   1999.09  [Refereed]

DOI

Structural Study of Aryl Selenides in Solution Based on77Se NMR Chemical Shifts:  Application of the GIAO Magnetic Shielding Tensor of the77Se Nucleus

Warô Nakanishi, Satoko Hayashi

The Journal of Physical Chemistry A ( American Chemical Society (ACS) )  103 ( 31 ) 6074 - 6081   1999.08  [Refereed]

DOI

Catalytic asymmetric reaction of lithium ester enolates with imines

Kiyoshi Tomioka, Hiroki Fujieda, Satoko Hayashi, Mostafa Ahmed Hussein, Takeshi Kambara, Yumiko Nomura, Motomu Kanai, Kenji Koga

Chemical Communications ( Royal Society of Chemistry )  ( 8 ) 715 - 716   1999.04  [Refereed]

　View Summary

An external chiral tridentate amino diether ligand 7 catalyzed the condensation reaction of a lithium ester enolate 2 with an imine 3 to give the enantiomerically enriched β-lactam 4 in high yield.

DOI

On the Stability and the Bonding Model of n→σ* Type Molecular Complexes, R2Z−X−X:  Proposal of 3c-4e Description for Z−X−X in the Adducts

Warô Nakanishi, Satoko Hayashi, Hiroshi Kihara

The Journal of Organic Chemistry ( American Chemical Society (ACS) )  64 ( 8 ) 2630 - 2637   1999.04  [Refereed]

DOI

Four-Center Six-Electron Interaction versus Lone Pair−Lone Pair Interaction between Selenium Atoms in Naphthalene Peri Positions

Warô Nakanishi, Satoko Hayashi, Shinji Toyota

The Journal of Organic Chemistry ( American Chemical Society (ACS) )  63 ( 24 ) 8790 - 8800   1998.11  [Refereed]

DOI

Why Selenoxanthone Gives an MC with Bromine:  An Examination of Electronic States of Xanthones and Xanthenes by Electron Spectroscopy and ab Initio MO Calculations

Warô Nakanishi, Satoko Hayashi, Yoshiaki Kusuyama, Takeshi Negoro, Shigeru Masuda, Hideki Mutoh

The Journal of Organic Chemistry ( American Chemical Society (ACS) )  63 ( 23 ) 8373 - 8379   1998.11  [Refereed]

DOI

On the Factors to Determine77Se NMR Chemical Shifts of Organic Selenium Compounds: Application of GIAO Magnetic Schielding Tensor to the77Se NMR Spectroscopy

Waro Nakanishi, Satoko Hayashi

Chemistry Letters ( The Chemical Society of Japan )  27 ( 6 ) 523 - 524   1998.06  [Refereed]

DOI

Attractive Interaction Caused by the Linear F···Se−C Alignment in Naphthalene Peri Positions

Warô Nakanishi, Satoko Hayashi, Akira Sakaue, Go Ono, Yuzo Kawada

Journal of the American Chemical Society ( American Chemical Society (ACS) )  120 ( 15 ) 3635 - 3640   1998.04  [Refereed]

DOI

Use of RAC-38, Carbonized Material of Fiber, for Teaching : As a Catalyst in the Decomposition of Hydrogen Peroxide

NAKANISHI Waro, INOUE Makoto, SAKAUE Akira, MIKAMI Shoko, HAYASHI Satoko

CHEMISTRY & EDUCATION ( The Chemical Society of Japan )  45 ( 3 ) 153 - 155   1997.03  [Refereed]

DOI

Inverse Substituent Effect on77Se NMR Chemical Shifts in Naphthalene Systems with Linear 4c-6e Se4Bond: 1-[8-(p-YC6H4Se)C10H6]SeSe[C10H6(SeC6H4Y-p)-8′]-1′vs. 1-(MeSe)-8-(p-YC6H4Se)C10H6

Warô Nakanishi, Satoko Hayashi, Hitomi Yamaguchi

Chemistry Letters ( The Chemical Society of Japan )  25 ( 11 ) 947 - 948   1996.11  [Refereed]

DOI

Structure of bis[8-(phenylselanyl)naphthyl] diselenide: first linear alignment of four Se atoms as a four-centre six-electron bond

War? Nakanishi, Satoko Hayashi, Shinji Toyota

Chemical Communications ( Royal Society of Chemistry (RSC) )  ( 3 ) 371 - 371   1996  [Refereed]

DOI

Evidence for the Equilibrium and Estimation of the Equilibrium Constants between Molecular Complexes and Trigonal Bipyramidal Adducts of Diaryl Selenide Dibromides in Solution

Waro Nakanishi, Satoko Hayashi

Chemistry Letters ( The Chemical Society of Japan )  24 ( 1 ) 75 - 76   1995.01  [Refereed]

DOI

Molecular Complex Formation of Diphenyl Selenides with Bromine. Electronic and Steric Requirements

Waro Nakanishi, Satoko Hayashi, Yosuke Nakamura, Hiizu Iwamura

Chemistry Letters ( The Chemical Society of Japan )  21 ( 5 ) 735 - 738   1992.05  [Refereed]

DOI

Molecular Complex Formation of Diphenyl Selenides with Bromine: Electronic and Steric Effects

Warō Nakanishi, Kazuyo Sakamoto, Kazumi Isaka, Satoko Hayashi

Phosphorus, Sulfur, and Silicon and the Related Elements ( Informa UK Limited )  67 ( 1-4 ) 79 - 82   1992.04  [Refereed]

DOI

自然科学に興味を抱かせる授業の試み -身近な物質「石炭」を利用した一例- 共著

中西和郎, 林聡子

化学と教育 日本化学会 ( 公益社団法人 日本化学会 )  40 ( 3 ) 191 - 191   1992.03  [Refereed]

DOI

MOLECULAR-COMPLEX FORMATION OF DIPHENYL SELENIDES WITH BROMINE - ELECTRONIC AND STERIC EFFECTS

W NAKANISHI, K SAKAMOTO, K ISAKA, S HAYASHI

PHOSPHORUS SULFUR AND SILICON AND THE RELATED ELEMENTS ( GORDON BREACH SCI PUBL LTD )  67 ( 1-4 ) 79 - 82   1992  [Refereed]

Short communication. Structural studies of bromine adducts of 1,2‐ and 1,4‐bis(phenylseleno)benzenes. Evidence for the (TB, MC) structure of 1,2‐(PhSeBr2)2C6H4

W. Nakanishi, Y. Okumura, S. Hayashi

Journal of Physical Organic Chemistry ( Wiley )  4 ( 8 ) 523 - 525   1991  [Refereed]

　View Summary

1,2‐Bis(phenylseleno)benzene reacted with equimolar amount of bromine to yield a trigonal bipyramidal (TB) adduct, in contrast to the molecular complex (MC) structure of selenanthrene with bromine. Whereas the structure of 1,4‐(PhSeBr2)2C6H4 was (TB, TB) at the two selenium atoms, that of the 1,2‐derivative was demonstrated to be (TB, MC), the first example of an MC structure of PhSeC6H4Y with Br2 [Y = 2‐PhBr2Se(TB)]. Both electronic and steric effects of the group must play an important role in MC formation. Rapid structural exchange in this tetrabromide, (TB, MC) ⇄ (MC, TB), was also observed. Copyright © 1991 John Wiley &amp
Sons Ltd.

DOI

Structural studies of halogen adducts of some cyclic selenides and tellurides by1H,13C,77Se and125Te NMR. Evidence for the formation of molecular complexes of selenoxanthone and selenanthrene with bromine

War? Nakanishi, Yasuhiro Yamamoto, Satoko Hayashi, Hideyuki Tukada, Hiizu Iwamura

Journal of Physical Organic Chemistry ( Wiley )  3 ( 6 ) 369 - 374   1990.06  [Refereed]

DOI

Structural studies of halogen adducts of diorganyl chalcogenides in solutions by1H,13C,77Se and125Te NMR

War? Nakanishi, Satoko Hayashi, Hideyuki Tukada, Hiizu Iwamura

Journal of Physical Organic Chemistry ( Wiley )  3 ( 6 ) 358 - 368   1990.06  [Refereed]

DOI