Synthesis, Structure, and Reactivity of Group VI Metal Complexes Bearing Group IV Metallocenyldiphosphine Moieties and a Pentamethylcyclopentadienyl Ligand

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• 作者：Takamasa Miyazaki ; Yoshiaki Tanabe ; Masahiro Yuki ; Yoshihiro Miyake ; Yoshiaki Nishibayashi
• 刊名：Organometallics
• 出版年：2013
• 出版时间：March 25, 2013
• 年：2013
• 卷：32
• 期：6
• 页码：2007-2013
• 全文大小：398K
• 年卷期：v.32,no.6(March 25, 2013)
• ISSN：1520-6041

文摘

A series of group VI metal complexes bearing a group IV metallocenyldiphosphine moiety and a pentamethylcyclopentadienyl ligand have been prepared and structurally characterized. Reactions of trinuclear complexes with KC₈ give the corresponding neutral chloride-bridged complexes. Further reaction of the resulting chloride-bridged complex with NaBAr^F₄ gives the corresponding monocationic chloride-bridged complex. On the other hand, reactions of the neutral chloride-bridged complexes with n-BuLi give the corresponding chloride-bridged alkyl complexes, where the group IV metallocene(III) moiety and the coordinatively unsaturated group VI metal(II) center are in close proximity. Spectroscopic and crystallographic studies of the reaction of a chloride-bridged alkyl complex with CO or a protic acid indicate that further disproportionation takes place at the alkyl zirconocene(III) moiety.