研究者詳細 - 林　聡子

論文 - 林　聡子

分割表示127 件中 61 - 80 件目／全件表示 >>

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年08月 [査読有り]

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.

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年07月 [査読有り]

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.

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年07月 [査読有り]

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.

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年05月 [査読有り]

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.

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年01月 [査読有り]

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.

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年 [査読有り]

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年09月 [査読有り]

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.

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 (担当区分：筆頭著者 )

Journal of Organic Chemistry ( American Chemical Society (ACS) ) 74 ( 13 ) 4763 - 4771 2009年07月 [査読有り]

(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.

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 (担当区分：筆頭著者 )

Phosphorus, Sulfur and Silicon and the Related Elements ( Informa UK Limited ) 184 ( 6 ) 1481 - 1495 2009年06月 [査読有り]

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.

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 (担当区分：筆頭著者 )

Bulletin of the Chemical Society of Japan ( The Chemical Society of Japan ) 82 ( 6 ) 712 - 722 2009年 [査読有り]

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.

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 (担当区分：筆頭著者 )

Bioinorganic Chemistry and Applications ( Hindawi Limited ) 2009 1 - 11 2009年 [査読有り]

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.

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年 [査読有り]

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年 [査読有り]

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 (担当区分：筆頭著者 )

New J. Chem. ( Royal Society of Chemistry (RSC) ) 33 ( 1 ) 196 - 206 2009年 [査読有り]

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年 [査読有り]

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.

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年12月 [査読有り]

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.

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

Hayashi Satoko, Nakanishi Waro (担当区分：筆頭著者 )

Bulletin of the Chemical Society of Japan ( Chemical Society of Japan ) 81 ( 12 ) 1605 - 1615 2008年12月 [査読有り]

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年12月 [査読有り]

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.

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年12月 [査読有り]

(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.

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年10月 [査読有り]

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