An Experimental Charge Density Study of Two Isomers of Hexasilabenzene

Kratzert, Daniel; Leusser, Dirk; Holstein, Julian J.; Dittrich, Birger; Abersfelder, Kai; Scheschkewitz, David; Stalke, Dietmar

doi:10.1002/anie.201209906

Cited by 52 publications

(32 citation statements)

References 64 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The topology analysis of high-resolution X-ray data of 12 is consistent with the resonance hybrid between 12¤ and 12¤¤. 28 The calculated NICS(0) values of model compound for 12 of ¹23.8 ppm are larger than that of benzene (ca. ¹10 ppm), which suggests that the central Si 4 moiety of 12 exhibits a significant aromatic character.…”

Section: B27supporting

confidence: 62%

“…The topology analysis of high-resolution X-ray data shows no bond critical point was found between Si1 and Si1¤ and there is a distinct valence shell charge concentration outside the silicon cage, suggesting significant biradical character of Si1 and Si1¤ atoms. 28 The distance between bridgehead silicon atoms without substituents (shown in boldface) in Si 11 compound 14 is 2.4976(9) ¡, which is much shorter than those of 7 and 13.…”

mentioning

confidence: 98%

See 1 more Smart Citation

Silicon Compounds with Inverted Geometry around Silicon Atoms

Iwamoto

Ishida

2014

Chemistry Letters

View full text Add to dashboard Cite

In the last decade, several stable silicon compounds with nonclassical inverted geometry around silicon atoms have been synthesized. Their unusual structures, bonding, and reactivity have been investigated extensively by X-ray analysis, spectroscopy, and theoretical calculations. In this highlight review, recent progress on chemistry of silicon compounds with inverted geometry around silicon atoms is summarized.

show abstract

Section: B27supporting

confidence: 62%

mentioning

confidence: 98%

Silicon Compounds with Inverted Geometry around Silicon Atoms

Iwamoto

Ishida

2014

Chemistry Letters

View full text Add to dashboard Cite

show abstract

“…3c) and the O(3)–Ni–O(4) plane (Fig. 3d)484950. The valence shell charge concentration (VSCC) region at the Ni(II) centre are located between the bond paths of the Ni–O(1) and the Ni–O(2) bonds on the O(1)–Ni–O(2) plane (Fig.…”

Section: Resultsmentioning

confidence: 99%

Naked d-orbital in a centrochiral Ni(II) complex as a catalyst for asymmetric [3+2] cycloaddition

et al. 2017

View full text Add to dashboard Cite

Chiral metal catalysts have been widely applied to asymmetric transformations. However, the electronic structure of the catalyst and how it contributes to the activation of the substrate is seldom investigated. Here, we report an empirical approach for providing insights into the catalytic activation process in the distorted Ni(II)-catalysed asymmetric [3+2] cycloaddition of α-ketoesters. We quantitatively characterize the bonding nature of the catalyst by means of electron density distribution analysis, showing that the distortion around the Ni(II) centre makes the dz2 orbital partially ‘naked', wherein the labile acetate ligand is coordinated with electrostatic interaction. The electron-deficient dz2 orbital and the acetate act together to deprotonate the α-ketoester, generating the (Λ)-Ni(II)–enolate. The solid and solution state analyses, together with theoretical calculations, strongly link the electronic structure of the centrochiral octahedral Ni(II) complex and its catalytic activity, depicting a cooperative mechanism of enolate binding and outer sphere hydrogen-bonding activation.

show abstract

“…For the past 200 years of the history of organic chemistry, benzene has fascinated and attracted experimental and theoretical chemists by its extraordinary properties. In contrast, hexasilabenzene (Si 6 H 6 ), which is the silicon analogue of benzene, has a nonplanar structure and has been a challenging target for synthesis . Therefore, it is worth comparing the structure and other properties of benzene with those of hexasilabenzene to realize the synthesis of the latter.…”

Section: Introductionmentioning

confidence: 99%

The planarity of heteroatom analogues of benzene: Energy component analysis and the planarization of hexasilabenzene

Nakamura

Kudo

2018

J Comput Chem

View full text Add to dashboard Cite

There are various nonplanar heteroatom analogues of benzene—cyclic 6π electron systems—and among them, hexasilabenzene (Si6H6) is well known as a typical example. To determine the factors that control their planarity, quantum chemical calculations and an energy component analysis were performed. The results show that the energy components mainly controlling the planarity of benzene and hexasilabenzene are different. For hexasilabenzene, electron repulsion energy was found to be significantly important for the planarity. The application of the pseudo Jahn–Teller effect and the Carter–Goddard–Malrieu–Trinquier model for the interpretation of the planarity of the benzene analogues was also investigated. Furthermore, based on the quantitative results, it was revealed that the planarization of hexasilabenzene is realized by introducing substituents with π‐accepting ability, such as the boryl group, that bring about a reduction of the π‐electron repulsion on the silicon skeleton. © 2018 Wiley Periodicals, Inc.

show abstract

An Experimental Charge Density Study of Two Isomers of Hexasilabenzene

Cited by 52 publications

References 64 publications

Silicon Compounds with Inverted Geometry around Silicon Atoms

Silicon Compounds with Inverted Geometry around Silicon Atoms

Naked d-orbital in a centrochiral Ni(II) complex as a catalyst for asymmetric [3+2] cycloaddition

The planarity of heteroatom analogues of benzene: Energy component analysis and the planarization of hexasilabenzene

Contact Info

Product

Resources

About