[2-(三硅基)苯]二硅烷与Ni(二乙膦基乙烷)(三乙膦)₂的反应：η²-(硅-氢)镍和四价镍-氢配合物的表征

Reaction of [2-(SiH3)C6H4]2SiH2 with Ni(Et2PCH2CH2PEt2)(PEt3)2: characterization of eta2-(Si-H)Ni and NiIV-H complexes.

作者信息

Chen Wanzhi, Shimada Shigeru, Tanaka Masato, Kobayashi Yuka, Saigo Kazuhiko

机构信息

National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba Central 5, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan.

出版信息

J Am Chem Soc. 2004 Jul 7;126(26):8072-3. doi: 10.1021/ja039244k.

DOI:10.1021/ja039244k

PMID:15225021

Abstract

The reaction of (2-SiH3C6H4)2SiH2 with Ni(Et2PCH2CH2PEt2)(PEt3)2 afforded a new silylnickel complex, which, in the solid state, was determined to be a bis(silyl)eta2-(Si-H)nickel complex, the first example of eta2-(Si-H)nickel complex by single-crystal X-ray analysis. Variable-temperature NMR spectroscopy revealed fluxional behavior of the complex in solution; at room temperature, exchange of five hydrogens (two SiH2 and one hydrogen bound to nickel) was observed, while at -80 degrees C the exchange of hydrogens appeared frozen to adopt a tris(silyl)(hydrido)nickel(IV) structure, which was confirmed by theoretical calculation. The latter complex is the first example of hydridonickel(IV) complex.

摘要

(2-硅氢基苯基)二硅烷与Ni(Et₂PCH₂CH₂PEt₂)(PEt₃)₂反应得到一种新的硅基镍配合物，通过单晶X射线分析确定其固态为双(硅基)η²-(Si-H)镍配合物，这是首例η²-(Si-H)镍配合物。变温核磁共振光谱表明该配合物在溶液中具有动态行为；室温下观察到五个氢（两个SiH₂和一个与镍相连的氢）发生交换，而在-80℃时氢的交换似乎冻结，呈现出三(硅基)(氢基)镍(IV)结构，这通过理论计算得到证实。后一种配合物是首例氢基镍(IV)配合物。