Abstract
1-Chloropentamethyl-1-silylgermane, ClSiMe2GeMe3 (1), and 1-chloromethylpentamethyl-1-silylgermane, ClCH2SiMe2GeMe3 (2), undergo Lewis acid-catalyzed rearrangements to ClGeMe2SiMe3 (3) and ClSiMe2CH2GeMe3 (4), respectively. Under similar conditions the isomeric ClGeMe2SiMe3 (3) undergoes a fragmentation reaction involving the formation of Me3SiCl and Me2GeCl2, and ClCH2GeMe2SiMe3 (5) rearranges to ClMe2GeCH2SiMe3 (6). Methyllithium treatment of Ph3SiGeMe3 and Me3SiGePh3 and [1,1‘]-tetramethylsilylgermylferrocenophane [(1,1‘-Me2SiMe2Ge((η5-C5H4)2Fe] results in methylation of the silicon atom and formation of the corresponding germyl anion. When the silicon−germanium-bonded fragment is incorporated into a bimetallic transition metal complex, i.e., (η5-C5H5)Fe(CO)2SiMe2GeMe2Fe(η5-C5H5)(CO)2 (7), base treatment with 1 equiv of lithium diisopropylamide (LDA) leads to predominance of silyl group migration to the cyclopentadienyl ring over germyl migration (9:1). Treatment of 7 with a 2.5 molar excess of LDA, fo...
Published Version
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