Mechanistic Aspects of Transition-Metal Catalyzed Dehydrogenative Silane Coupling Reactions
Mechanistic Aspects of Transition-Metal Catalyzed Dehydrogenative Silane Coupling Reactions
复制标题
过渡金属催化脱氢硅烷偶联反应的机理
DOI：
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发表时间：
1990
期刊：
影响因子：
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通讯作者：
T. Don Tilley
中科院分区：
文献类型：
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作者：
T. Don Tilley
一些过渡金属配合物催化硅烷脱氢偶联得到硅-硅键化合物。基于过渡金属硅烯配合物LnM = SiR2的机制似乎可能用于其中一些反应；然而，几乎没有证据支持它们参与已知的系统。基于化学计量反应中存在的先例，晚期过渡金属催化剂更可能的机制是氧化加成/还原消除循环。对于早期过渡金属（d°）催化剂，迄今为止积累的证据指向基于协调的4中心过渡态的“σ键重分解”机制。
Abstract Dehydrogenative silane couplings to give Si-Si bonded compounds are catalyzed by a number of transition-metal complexes. A mechanism based on transition-metal silylene complexes, LnM = SiR2, seems possible for some of these reactions; however, little evidence exists to support their involvement in known systems. Based on precedents that exist in stoichiometric reactions, a more likely mechanism for late transition-metal catalysts consists of oxidative addition/reductive elimination cycles. For early transition metal (d°) catalysts, evidence accumulated to date points toward a “σ-bond metathesis” mechanism based on concerted, 4-center transition states.