Synthesis, Structure, and Reactions of a (η^3-α-silabenzyl)molybdenum Complex: A Synthetic Equivalent of a Coordinatively Unsaturated Silyl Complex
Synthesis, Structure, and Reactions of a (η^3-α-silabenzyl)molybdenum Complex: A Synthetic Equivalent of a Coordinatively Unsaturated Silyl Complex
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(η^3-α-硅苄基)钼配合物的合成、结构和反应：配位不饱和硅基配合物的合成等价物
DOI：
10.1021/om400225j
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发表时间：
2013
期刊：
影响因子：
2.8
通讯作者：
小室貴士,菅野雄斗,飛田博実
中科院分区：
文献类型：
--
作者：
Y. Maeda;T. Akasaka;S.N. Tagmatarchis;小室貴士,菅野雄斗,飛田博実
用BPh 3从（芳基硅烷基）（DMAP）钼配合物Cp* Mo（CO）2（DMAP）{Si（p-Tol）3}（2）中除去4-（二甲氨基）吡啶（DMAP），高产率地合成了（η3-α-硅苄基）钼配合物Cp*Mo（CO）2{η3（Si，C，C）-Si（p-Tol）3}（1; Cp* = η5-C5 Me 5，p-Tol = p-C6 H4 Me）。通过（DMAP）（甲基）钼配合物Cp*Mo（CO）2（DMAP）Me（3）与三对甲苯基硅烷（HSi（p-Tol）3）通过甲烷消除反应容易地制备前体络合物2。研究了配合物1对DMAP和腈的反应性，结果表明配合物1是16电子硅基配合物Cp*Mo（CO）2{Si（p-Tol）3}的合成等价物。因此，配合物1与DMAP在室温下定量反应，通过解离与钼配位的芳烃碳原子，生成芳基硅烷基配合物2。配合物1在室温下也与乙腈反应，通过Mo-C（芳烃）键的断裂和腈的插入，得到N-硅亚胺酰基配合物Cp*Mo（CO）2{η2（C，N）-C（Me）<$NSi（p-Tol）3}（4）。
The (η3-α-silabenzyl)molybdenum complex Cp*Mo(CO)2{η3(Si,C,C)-Si(p-Tol)3} (1; Cp* = η5-C5Me5,p-Tol =p-C6H4Me) was synthesized in high yield by removal of 4-(dimethylamino)pyridine (DMAP) from the (arylsilyl)(DMAP)molybdenum complex Cp*Mo(CO)2(DMAP){Si(p-Tol)3} (2) with BPh3. The precursor, complex2, was readily prepared by reaction of the (DMAP)(methyl)molybdenum complex Cp*Mo(CO)2(DMAP)Me (3) with tri-p-tolylsilane (HSi(p-Tol)3) through methane elimination. Study on the reactivity of1toward DMAP and nitrile revealed that complex1serves as a synthetic equivalent of the 16-electron silyl complex Cp*Mo(CO)2{Si(p-Tol)3}. Thus, complex1reacted with DMAP quantitatively at room temperature to reproduce arylsilyl complex2through dissociation of the arene carbon atoms coordinated to molybdenum. Complex1also reacted with acetonitrile at room temperature to give theN-silyliminoacyl complex Cp*Mo(CO)2{η2(C,N)-C(Me)NSi(p-Tol)3} (4) exclusively via cleavage of the Mo–C(arene) bonds followed by insertion of nitrile into the Mo–Si bond.