A Cation-Captured Palladium(0) Anion: Synthesis, Structure, and Bonding of [PdBr(PPh3)2]- Ligated by an N-Heterocyclic Phosphenium Cation

被引：44

作者：

Caputo, Christine A. ^{[1
]}

Brazeau, Allison L. ^{[1
]}

Hynes, Zachery ^{[1
]}

Price, Jacquelyn T. ^{[1
]}

Tuononen, Heikki M. ^{[2
]}

Jones, Nathan D. ^{[1
]}

机构：

[1] Univ Western Ontario, Dept Chem, London, ON N6A 5B7, Canada

[2] Univ Jyvaskyla, Dept Chem, FI-40014 Jyvaskyla, Finland

来源：

ORGANOMETALLICS | 2009年 / 28卷 / 17期

基金：

加拿大自然科学与工程研究理事会;

关键词：

OXIDATIVE ADDITION; PHOSPHORUS ANALOGS; CL BOND; COMPLEXES; CARBENES; IONS; REACTIVITY; CATALYSTS; HALIDE; PD(0);

D O I：

10.1021/om9006278

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Unsaturated N-heterocyclic phosphenium cations (uNHP) stabilize the [Pd-0(PR3)(2)X](-) anion proposed over the past decade to be the crucial but elusive intermediate in palladium-catalyzed cross-coupling reactions (X = halide). Insertion of metal into the P-Br bond of the precursor mesityl-substituted bromophosphine gives the structurally characterized Pd(0)-phosphenium complex (uNHP(Mes))Pd(PPh3)(2)Br, which features a long Pd-Br bond (2.7240(9) angstrom) and the shortest known Pd-P bond (2.1166(17) angstrom). The reaction is proposed to proceed by an associative pathway involving a Pd-bromophosphine complex that undergoes P-to-Pd bromide transfer.

引用

页码：5261 / 5265

页数：5

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