Unexpected Formation of Early Late Heterobimetallic Complexes from Transition Metal Frustrated Lewis Pairs

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• 作者：Andy M. Chapman ; Stephanie R. Flynn ; Duncan F. Wass
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：February 1, 2016
• 年：2016
• 卷：55
• 期：3
• 页码：1017-1021
• 全文大小：319K
• ISSN：1520-510X

文摘

Reaction of transition metal “frustrated” Lewis pair compounds of the type [Cp₂Zr(Me)(OC(CF₃)₂CH₂P^tBu₂)] with the low valent platinum species [Pt(norbornene)₃] leads to the unexpected formation of a heterobimetallic species [Cp₂Zr{Pt(Me)}(OC(CF₃)₂CH₂P^tBu₂)]. Single crystal X-ray analysis reveals an unusual T-shaped geometry at the platinum center, with a relevant C–Pt–P angle of 163.3(3)°. Treatment of this compound with PMe₃ yields [Pt(PMe₃)₄] and regenerates the zirconium precursor. Treatment with [(Et₂O)₂H][B(C₆F₅)₄] protonates off the methyl ligand to give an ether adduct at platinum. Analogous observations are made with titanium–platinum species. We propose the chemistry is best rationalized as a formal insertion of Pt(0) into a Zr–C or Ti–Cl bond.