Gold(III) Alkyne Complexes: Bonding and Reaction Pathways

被引：48

作者：

Rocchigiani, Luca ^{[1
]}

Fernandez-Cestau, Julio ^{[1
]}

Agonigi, Gabriele ^{[1
]}

Chambrier, Isabelle ^{[1
]}

Budzelaar, Peter H. M. ^{[2
]}

Bochmann, Manfred ^{[1
]}

机构：

[1] Univ East Anglia, Sch Chem, Norwich Res Pk, Norwich NR4 7TJ, Norfolk, England

[2] Univ Naples Federico II, Dept Chem, Via Cintia, I-80126 Naples, Italy

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2017年 / 56卷 / 44期

基金：

欧洲研究理事会;

关键词：

alkynes; density functional calculations; gold; homogeneous catalysis; reaction mechanisms; REDUCTIVE ELIMINATION; GOLD; INSERTION; ACTIVATION; CATALYSIS; PLATINUM;

D O I：

10.1002/anie.201708640

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The synthesis and characterization of hitherto hypothetical Au-III p-alkyne complexes is reported. Bonding and stability depend strongly on the trans effect and steric factors. Bonding characteristics shed light on the reasons for the very different stabilities between the classical alkyne complexes of PtII and their drastically more reactive AuIII congeners. Lack of back-bonding facilitates alkyne slippage, which is energetically less costly for gold than for platinum and explains the propensity of gold to facilitate C-C bond formation. Cycloaddition followed by aryl migration and reductive deprotonation is presented as a new reaction sequence in gold chemistry.

引用

页码：13861 / 13865

页数：5

共 56 条

[1]

[Anonymous], 2013, ANGEW CHEM

[2] Gold-catalysed reactions of diynes [J].