Published Papers - HAYASHI Satoko

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]

DOI

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]

DOI

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]

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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.

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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.

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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.

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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>

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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.

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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]

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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).

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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>

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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]

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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.

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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.

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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>

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