Synthesis of a 1-Aryl-2,2-chlorosilyl(phospha)silene Coordinated by an N-Heterocyclic Carbene.

Andreas Kyri,Shigeru Nagase,Jing-Dong Guo,Rainer Streubel,Takahiro Sasamori,Paresh Majhi,Vitaly Nesterov,Tomohiro Agou,Norihiro Tokitoh

doi:10.3390/molecules21101309

Andreas Kyri, Shigeru Nagase + Show 7 more

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https://doi.org/10.3390/molecules21101309

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Abstract

Phosphasilenes, P=Si doubly bonded compounds, have received considerable attention due to their unique physical and chemical properties. We report on the synthesis and structure of a chlorophosphasilene coordinated by an N-heterocyclic carbene (NHC), which has the potential of functionalization at the Si–Cl moiety. Treatment of a silylphosphine, ArPH–SiCl2RSi (Ar = bulky aryl group, RSi = Si(SiMe3)3) with two equivalents of Im-Me4 (1,3,4,5-tetramethylimidazol-2-ylidene) afforded the corresponding NHC-coordinated phosphasilene, ArP=SiClRSi(Im-Me4) as a stable compound. Bonding properties of the P=Si bond coordinated to an NHC will be discussed on the basis of theoretical calculations.

Highlights

There has been much interest in the chemistry of multiple bond compounds between heavier main group elements due to their unique π-electron systems different from those of second row elements such as olefin, imine, and azo compounds
It is evidenced that even the N-heterocyclic carbene (NHC)-adduct 11a exhibited P=Si multiple bond character in which, on the basis of theoretical calculations, a d-orbital of the Si atom is involved
Acknowledgments: This study shows part of the achievements from the Japan Society for the Promotion of Science (JSPS)-DAAD bilateral program between

Summary

Introduction

There has been much interest in the chemistry of multiple bond compounds between heavier main group elements due to their unique π-electron systems different from those of second row elements such as olefin, imine, and azo compounds. Phosphasilenes have generated much interest as heteronuclear π bond compounds between heavier group 14 and 15 elements in the expectation of their variety of electronic, optical, and magnetic properties when they are “functionalized” by further functional groups [13,14,15,16,17,18,19,20]. In this context, Tamao et al have reported the synthesis of π-functionalized phosphasilenes with organic π-conjugated systems (2, 3) and their Au complexes (Scheme 1) [21,22]

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