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首页> 外文期刊>Organometallics >A bis(silyl)nickel complex containing an o-carboranylene and its application in facile double silylation of alkynes and alkenes
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A bis(silyl)nickel complex containing an o-carboranylene and its application in facile double silylation of alkynes and alkenes

机译：含邻碳戊二烯的双（甲硅烷基）镍配合物及其在炔烃和烯烃的简便双甲硅烷基化中的应用

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摘要

The reaction of 1,2-bis(dimethylsilyl)carborane (1) with Ni(PEt3)(4) yielded the cyclic bis-(silyl)nickel complex (2). 2 was found to be a good catalyst for the double silylation reaction of alkynes and alkenes. Thus, the reaction of 1 with RC=CR' in the presence of a catalytic amount of 2 afforded the six-membered disilylene ring compounds o-B10H10C2(SiMe2)(2)(RC=CR') (R = R'= Ph (3); R = Ph, R'= H (4); R = R'= Pt (5); R = Ph, R'= Me (6); R = R'= Me (7)). In contrast, the reaction of 1-phenyl-2-(trimethylsilyl)acetylene with 1 in the presence of a catalytic amount of 2 afforded the six-membered disilylene ring compound (9) and the five-membered disilylene ring compound (10). The stoichiometric reaction of 2 with an active alkyne such as dimethyl acetylenedicarboxylate gave the six-membered disilylene ring compound (11). The intermedate 2 also was found to be a good catalyst for the double silylation of some alkenes. Thus, the reaction of 1 with 4-vinylanisole in the presence of a catalytic amount of 2 afforded the five-membered disilylene ring compound (15). However, treatment of 1 with 1,1-diphenylethylene under the same reaction conditions yielded a different type of five-membered disilylene ring compound (17). The reaction of 1 with 2,3-dimethylbutadiene in the presence of the nickel catalyst also was studied. The crystal structures of 2, 9, and 14 are described. [References: 45]
机译：1,2-双（二甲基甲硅烷基）碳烷（1）与Ni（PEt3）（4）的反应产生环状双-（甲硅烷基）镍络合物（2）。发现2是炔烃和烯烃的双甲硅烷基化反应的良好催化剂。因此，在催化量为2的存在下，1与RC = CR'的反应得到六元二甲硅烷基环化合物o-B10H10C2（SiMe2）（2）（RC = CR'）（R = R'= Ph （3）; R ＝ Ph，R′＝ H（4）; R ＝ R′＝ Pt（5）; R ＝ Ph，R′＝ Me（6）; R ＝ R′＝ Me（7））。相反，在催化量为2的存在下，1-苯基-2-（三甲基甲硅烷基）乙炔与1的反应得到六元二甲硅烷基环化合物（9）和五元二甲硅烷基环化合物（10）。 2与活性炔烃如乙炔二甲酸二甲酯的化学计量反应得到六元二甲硅烷基环化合物（11）。还发现中间体2是某些烯烃双甲硅烷基化的良好催化剂。因此，在催化量2的存在下，1与4-乙烯基茴香醚的反应得到五元二甲硅烷基环化合物（15）。然而，在相同的反应条件下用1，1-二苯基乙烯处理1得到了不同类型的五元二甲硅烷基环化合物（17）。还研究了镍催化剂存在下1与2，3-二甲基丁二烯的反应。描述了2、9和14的晶体结构。 [参考：45]

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