Mononuclear Heteroscorpionate Zwitterionic Zinc Terminal Hydride: Synthesis, Reactivity, and Catalysis for Hydrosilylation of Aldehydes
writer：Zehuai Mou, Hongyan Xie, Meiyan Wang, Na Liu, Changguang Yao, Lei Li, Jingyao Liu, Shihui Li and Don
keywords：lutetium; complex; insertion; activation; metalation
source：期刊
specific source：http://pubs.acs.org/doi/pdf/10.1021/acs.organomet.5b00413
Issue time：2015年
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═S insertion into the Zn–H 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.
