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Ab initio MO and DFT study for the isomerisation of bicyclo[1.1.0]tetrasilane and the germanium analogues

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Abstract

The mechanism of the unimolecular isomerisation reaction of the silicon and germanium analogues of bicyclo[1.1.0]butane with various kinds of substituents (X4R6; X = Si and Ge, R=H, CH3, t-Bu and SiH3) to the corresponding cyclobutene analogues has been investigated by ab initio molecular orbital and DFT methods. Several reaction mechanisms were considered. They are roughly divided into two types; (1) skeletal rearrangement and (2) substituent migration. It was found that substituents (R) have the leading effect on the reaction mechanism but the partial or full replacement of the skeletal silicon atoms by germanium atoms has some important effects as well. Furthermore, the character of the bridge bond of the long-bond and short-bond isomers of these bicyclic compounds was investigated and discussed in comparison with the π bond in ethene and disilene by the CiLC analysis.

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Acknowledgments

We (Y.K. and T.K.) would like to thank Prof. Soichiro Kyushin and Dr. Kimio Yoshimura for the information of the experiments and their valuable discussions. This work has been supported by a Grant-in-Aid on Priority-Area-Research: Molecular Theory for Real Systems (461) (T.K. and S.S.).

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Authors and Affiliations

  1. Department of Chemistry and Chemical Biology, Graduate School of Engineering, Gunma University, 1-5-1 Tenjin-cho, Kiryu, 376-8515, Japan

    Y. Konno & T. Kudo

  2. Department of Chemistry, Faculty of Engineering, Gifu University, 1-1 Yanagido, Gifu, 501-1193, Japan

    S. Sakai

Authors
  1. Y. Konno
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  2. T. Kudo
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  3. S. Sakai
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Correspondence to T. Kudo.

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Dedicated to Professor Shigeru Nagase on the occasion of his 65th birthday and published as part of the Nagase Festschrift Issue.

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Konno, Y., Kudo, T. & Sakai, S. Ab initio MO and DFT study for the isomerisation of bicyclo[1.1.0]tetrasilane and the germanium analogues. Theor Chem Acc 130, 371–383 (2011). https://doi.org/10.1007/s00214-011-1001-1

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