Activation of 7-Silanorbornadienes by N-Heterocyclic Carbenes: A Selective Way to N-Heterocyclic-Carbene-Stabilized Silylenes.
Activation of 7-Silanorbornadienes by N-Heterocyclic Carbenes: A Selective Way to N-Heterocyclic-Carbene-Stabilized Silylenes.
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DOI：
10.1021/jacs.6b02824
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发表时间：
2016-04
影响因子：
15
通讯作者：
Dennis Lutters;C. Severin;M. Schmidtmann;T. Müller
中科院分区：
文献类型：
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作者：
Dennis Lutters;C. Severin;M. Schmidtmann;T. Müller
报道了n -杂环羰基（NHC） ImMe4稳定的Ter(H)Si: 3a （Ter: 2,6-二（2,4,6-三甲基苯基）苯基）和Ter*(H)Si: 3b （Ter*: 2,6-二（2,4,6-三异丙基苯基）苯基）的合成。稳定氢化硅氧烷3的合成是由以前未知的nhc诱导的硅降冰片二烯衍生物的断裂完成的。对稳定的硅烯3及其Fe(CO)4配合物12的结构研究以及它们成键情况的理论分析表明，稳定的硅烯3可以看作是中性的硅基阴离子等价物。对反应过程的计算研究表明，NHC与硅降冰片二烯之间的反应实际上是一步反应。对该反应范围和局限性的理论评估表明，它是一般的，也可用于合成其他碳类似物，如革烯和膦烯。
The synthesis of hydridosilylenes Ter(H)Si: 3a (Ter: 2,6-bis(2,4,6-trimethylphenyl)phenyl) and Ter*(H)Si: 3b (Ter*: 2,6-bis(2,4,6-triiso-propylphenyl)phenyl) stabilized by the N-heterocyclic carbene (NHC) ImMe4 is reported. The synthesis of stabilized hydridosilylenes 3 was accomplished by a previously unknown NHC-induced fragmentation of silanorbornadiene derivatives. Structural studies of the stabilized silylenes 3 and of its Fe(CO)4 complex 12 accompanied by a theoretical analysis of their bonding situation indicate that stabilized silylenes such as 3 can be regarded as neutral silyl anion equivalents. A computational investigation of the reaction course indicate a virtual one-step reaction between the NHC and the silanorbornadiene. A theoretical assessment of the scope and limitations of this reaction suggests that it is general and can be used also for the synthesis of other carbene analogues such as germylenes and phosphinidenes.