Mononuclear Heteroscorpionate Zwitterionic Zinc Terminal Hydride: Synthesis, Reactivity, and Catalysis for Hydrosilylation of Aldehydes

详细信息    查看全文

• 作者：Zehuai Mou ; Hongyan Xie ; Meiyan Wang ; Na Liu ; Changguang Yao ; Lei Li ; Jingyao Liu ; Shihui Li ; Dongmei Cui
• 刊名：Organometallics
• 出版年：2015
• 出版时间：August 24, 2015
• 年：2015
• 卷：34
• 期：16
• 页码：3944-3949
• 全文大小：348K
• ISSN：1520-6041

文摘

Treatment of heteroscorpionate zinc benzyloxy complex LZnOBn (1, L = (^MePz)₂CP(Ph)₂NPh, ^MePz = 3,5-dimethylpyrazolyl) with phenylsilane (PhSiH₃) gave a zinc hydride complex LZnH (2) containing a rare terminal hydride fragment. X-ray diffraction analysis and the DFT calculation confirm the zwitterionic structure of complex 2. The stoichiometric reaction of 2 with CS₂ readily afforded a dithioformate complex LZnSCH(S) (3) of the C鈺怱 insertion into the Zn鈥揌 product. Moreover, complex 2 was an efficient catalyst for the hydrosilylation reaction of a series of silanes and aldehydes under mild conditions, featuring excellent functional group tolerance. The preliminary mechanistic study revealed that both zinc benzyloxy complex 1 and zinc hydride complex 2 were involved in the hydrosilylation process as the reaction intermediates.