Synthesis, Structure, and Bonding Nature of Ethynediyl-Bridged Bis(silylene) Dinuclear Complexes of Tungsten and Molybdenum
Synthesis, Structure, and Bonding Nature of Ethynediyl-Bridged Bis(silylene) Dinuclear Complexes of Tungsten and Molybdenum
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DOI：
10.1021/om200096z
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发表时间：
2011-08
期刊：
影响因子：
2.8
通讯作者：
H. Sakaba;H. Oike;M. Kawai;Masato Takami;C. Kabuto;M. Ray;Y. Nakao;Hirofumi Sato;S. Sakaki
中科院分区：
文献类型：
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作者：
H. Sakaba;H. Oike;M. Kawai;Masato Takami;C. Kabuto;M. Ray;Y. Nakao;Hirofumi Sato;S. Sakaki
Ph2HSiC≡CSiHPh2与2种等量的不稳定络合物Cp*(CO)2M(NCMe)Me （1a, M = W; 2, M = Mo; Cp* = η5-C5Me5）反应得到新型cc桥接双核络合物Cp*(CO)2M(SiPh2)(μ-CC)(SiPh2)M(CO)2Cp* (5, M = W; 6, M = Mo)，其分子结构由x射线晶体学测定。CC桥与两个Cp*(CO)2M（SiPh2）片段的金属中心和硅烯中心相互作用，形成两个M-Si-C三环骨架，它们几乎垂直相连。5的W-Si键距与典型的碱稳定钨硅烯配合物的键距相当。C - C键的距离比典型的C≡C三键的距离长得多，并且与典型的C = C双键的距离相似。用DFT研究了模型络合物Cp(CO)2W(SiH2)(μ-CC)(SiH2)W(CO)2Cp (5M; Cp η5-C5H5)，揭示了5的成键性质和电子结构。研究表明，5M是一种由乙炔二烷基桥接的双（硅烯）双核钨配合物，含有多种c…
Reactions of Ph2HSiC≡CSiHPh2 with 2 equiv of the labile complexes Cp*(CO)2M(NCMe)Me (1a, M ═ W; 2, M ═ Mo; Cp* ═ η5-C5Me5) gave the novel CC-bridged dinuclear complexes Cp*(CO)2M(SiPh2)(μ-CC)(SiPh2)M(CO)2Cp* (5, M ═ W; 6, M ═ Mo), whose molecular structures were determined by X-ray crystallography. The CC bridge interacts with both the metal and silylene centers of two Cp*(CO)2M(SiPh2) fragments to form two M–Si–C three-membered-ring skeletons which are linked nearly perpendicularly to each other. The W–Si bond distances of 5 are comparable to those of typical base-stabilized tungsten silylene complexes. The C–C bond distance is much longer than a typical C≡C triple-bond distance and is similar to a typical C═C double-bond distance. The bonding nature and electronic structure of 5 were disclosed by a DFT study of the model complex Cp(CO)2W(SiH2)(μ-CC)(SiH2)W(CO)2Cp (5M; Cp ═ η5-C5H5). This study demonstrates that 5M is an ethynediyl-bridged bis(silylene) dinuclear tungsten complex which contains various c...