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

被引：24

作者：

Jian, Zhongbao ^{[1
]}

Daniliuc, Constantin G. ^{[1
]}

Kehr, Gerald ^{[1
]}

Erker, Gerhard ^{[1
]}

机构：

[1] Westfal Wilhelms Univ Munster, Organ Chem Inst, Corrensstr 40, D-48149 Munster, Germany

来源：

ORGANOMETALLICS | 2017年 / 36卷 / 02期

基金：

欧洲研究理事会;

关键词：

ZIRCONOCENE-PHOSPHINOARYLOXIDE COMPLEXES; SMALL-MOLECULE ACTIVATION; FREE HYDROGEN ACTIVATION; POLYMERIZATION CATALYSTS; OLEFIN POLYMERIZATION; HETEROLYTIC CLEAVAGE; STEREOSELECTIVE HYDROGENATION; C-H; REACTIVITY; ZIRCONIUM;

D O I：

10.1021/acs.organomet.6b00828

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

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 a bond of the FLP 10 remains intact in these reactions. Complex 10 splits dihydrogen, but subsequently the Zr-C sigma 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) sigma-bond of the Zr+/P system 10.

引用

页码：424 / 434

页数：11

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