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The thermally stable [(tBuMe2Si)2M] (M=Zn, Hg) generate R3Si. radicals in the presence of [(dmpe)Pt(PEt3)2] at 60–80 °C. The reaction proceeds via hexacoordinate Pt complexes, (M=Zn (2 a and 2 b), M=Hg (3 a and 3 b)) which were isolated and characterized. Mild warming or photolysis of 2 or 3 lead to homolytic dissociation of the PtMSiR3 bond generating silyl radicals and novel unstable pentacoordinate...
Si‐H‐Bindungen können durch Organozink‐ und Silylzinkverbindungen in Gegenwart von Spuren von Radikalstartern wie tBu2Hg oder AIBN aktiviert werden. Dabei entstehen in guten Ausbeuten Zinkiosilane (siehe Schema). Werden Dihydridosilane eingesetzt, erhält man geminale Dizinkiosilane. Auch Zinkio‐verbrückte Disilyllithiumverbindungen mit drei (1) und vier Metall‐Silicium‐Bindungen wurden synthetisiert.
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