The reaction of 1-methyl-3-trimethylsilylimidazoline-2-thione with hexachlorodisilane proceeds toward substitution of four of the disilane Cl atoms during the formation of disilicon complexes with two neighboring hexacoordinate Si atoms. The N,S-bidentate methimazolide moieties adopt a buttressing role, thus forming paddlewheel-shaped complexes of the type CISi(μ-mt)4 SiCl (mt=methimazolyl). Most interestingly, three isomers (i.e., with (CIN4)Si-Si(S4Cl), (CIN3S)Si-Si(S3NCI), and (CIN2S2)Si-Si(S2N2CI) skeletons as so-called (4,0), (3,1), and cis-(2,2) paddlewheels) were detected in solution by using29Si NMR spectroscopic analysis. Two of these isomers could be isolated as crystalline solids, thus allowing their molecular structures to be analyzed by using X-ray diffraction studies. In accord with time-dependent NMR spectroscopy, computational analyses proved the cis-(2,2) isomer with a (CIN2S2)Si-Si(S2N2CI) skeleton to be the most stable. The compounds presented herein are the first examples of crystallographically evidenced disilicon complexes with two Si-Si-bonded octahedrally coordinated Si atoms and representatives of the still scarcely explored class of Si coordination compounds with sulfur donor atoms.
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© 2013 Wiley-VCH Verlag 14024 GmbH&Co. KGaA, Weinheim.
All Science Journal Classification (ASJC) codes
- Organic Chemistry