研究者詳細 - 林　聡子

Acta Crystallographica Section B: Structural Science, Crystal Engineering and Materials ( International Union of Crystallography ) 73 ( 2 ) 265 - 275 2017年04月 [査読有り] [招待有り]

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).

DOI

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

Cristina Mitrofan, Thorsten Gust, Andreas Zanin, Roxana M. Bï¿½rzoi, 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年04月 [査読有り]

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.

DOI

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 (担当区分：筆頭著者 )

Journal of Physical Chemistry A ( American Chemical Society ) 121 ( 12 ) 2482 - 2496 2017年03月 [査読有り]

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年01月 [査読有り]

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年01月 [査読有り]

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年09月 [査読有り]

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年08月 [査読有り]

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年07月 [査読有り]

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 (担当区分：筆頭著者 )

RSC Advances ( Royal Society of Chemistry (RSC) ) 6 ( 55 ) 49651 - 49660 2016年04月 [査読有り]

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年04月 [査読有り]

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 (担当区分：筆頭著者 )

Journal of Organic Chemistry ( American Chemical Society ) 80 ( 24 ) 11963 - 11976 2015年12月 [査読有り]

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 (担当区分：筆頭著者 )

Physical Chemistry Chemical Physics ( Royal Society of Chemistry (RSC) ) 18 ( 15 ) 9948 - 9960 2015年12月 [査読有り]

DOI

　前のページ - 次のページ　

<林 聡子>

論文 - 林 聡子

<林　聡子>

論文 - 林　聡子