American Chemical Society
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Frustrated Lewis Pair vs Metal–Carbon σ‑Bond Insertion Chemistry at an o‑Phenylene-Bridged Cp2Zr+/PPh2 System

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journal contribution
posted on 2017-01-09, 15:21 authored by Zhongbao Jian, Constantin G. Daniliuc, Gerald Kehr, Gerhard Erker
Methyl anion abstraction from (o-diphenylphosphino)­phenyl­(methyl)­zirconocene by trityl tetrakis­(pentafluorophenyl)­borate gives the o-phenylene-bridged Zr+/P system 10. It behaves toward a variety of reagents as a typical Zr+/P frustrated Lewis pair (FLP). It undergoes cooperative 1,4-addition reactions to some chalcone derivatives and adds in a 1,2-fashion to a variety of organic carbonyls and to several heterocumulenes. The reactive Zr–C σ bond of the FLP 10 remains intact in these reactions. Complex 10 splits dihydrogen, but subsequently the Zr–C σ bond is protonolytically cleaved in this case. Only a few special reagents, among them carbon monoxide, undergo the usual insertion reaction into the Zr–C­(aryl) σ-bond of the Zr+/P system 10.