Die chemie der schweren carben-analogen R2M,M = Si,Ge, Sn: X. 7-sila-norbornadiene: reaktionen mit halogenen und thermolyse in genewart von metallorganischen oder organischen halogeniden |
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| Institution: | 1. Department of Materials Science and Technology, Faculty of Engineering, Gifu University, 1-1 Yanagido, Gifu 501-1193, Japan;2. Department of Chemistry and Biomolecular Science, Faculty of Engineering, Gifu University, 1-1 Yanagido, Gifu 501-1193, Japan;1. School of Chemistry & Chemical Engineering, Yangzhou University, Yangzhou, 225009, China;2. School of Environmental and Chemical Engineering, Jiangsu University of Science and Technology, Zhenjiang, 212003, China;1. Cell, Molecular, and Structural Biology Graduate Program, Miami University, Oxford, OH 45056, United States;2. Department of Chemistry and Biochemistry, Miami University, Oxford, OH 45056, United States;1. A.N. Nesmeyanov Institute of Organoelement Compounds RAS, Moscow, Russia;2. Enikolopov Institute of Synthetic Polymeric Materials RAS, Moscow, Russia;1. Key Laboratory of Pesticide & Chemical Biology of Ministry of Education, International Joint Research Center for Intelligent Biosensor Technology and Health, College of Chemistry, Chemical Biology Center, Central China Normal University, Wuhan 430079, PR China;2. Collaborative Innovation Center of Chemical Science and Engineering, Tianjin 300071, PR China |
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| Abstract: | The 7-sila norbornadienes (I–IV) react rapidly with halogens at −20 to +20°C to yield Me2SiHal2 (Hal = Cl, Br, I) and the naphthalene or benzene derivatives (V–VIII). Bromine in CCl4 at 0°C, however, caused surprising rearrangement in I giving the 2-bromosilylated naphthalene (IX), since an attack at the alkene group seemed to be preferred. Methylation and methoxylation of IX gave respectively X and XI. Careful hydrolysis of IX yielded the disiloxane VII. Insertions of Me2Si into the SiHal, SiH, SiC, or SnC bonds were not observed at 160–200°C, whereas insertions into SnCl or SnH bonds occurred smoothly via a one-step mechanism. Halogen is abstracted from different CHal bonds leading to Me2SiHal2 and sometimes to Me4Si2Hal2. The degradation of the silylene precursors in these cases is always first order and resembles that of spontaneous thermolysis. |
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