Oxidative Addition of Aryl Electrophiles to a Prototypical Nickel(0) Complex: Mechanism and Structure/Reactivity Relationships

被引：140

作者：

Bajo, Sonia ^{[1
,3
]}

Laidlaw, Gillian ^{[1
]}

Kennedy, Alan R. ^{[1
]}

Sproules, Stephen ^{[2
]}

Nelson, David J. ^{[1
]}

机构：

[1] Univ Strathclyde, WestCHEM Dept Pure & Appl Chem, Thomas Graham Bldg,295 Cathedral St, Glasgow G1 1XL, Lanark, Scotland

[2] Univ Glasgow, WestCHEM Sch Chem, Univ Pl, Glasgow G12 8QQ, Lanark, Scotland

[3] Univ Zaragoza, Dept Quim Inorgan, ISQCH, Ctr Innovac Quim Avanzada ORFEO CINQA,CSIC, E-50009 Zaragoza, Spain

来源：

ORGANOMETALLICS | 2017年 / 36卷 / 08期

基金：

英国工程与自然科学研究理事会;

关键词：

TRANSITION-METAL-COMPLEXES; C-O BONDS; ZEROVALENT PALLADIUM COMPLEXES; CROSS-COUPLING REACTIONS; SUZUKI-MIYAURA REACTION; CATALYZED TRIFLUOROMETHYLTHIOLATION; PHOTOREDOX CATALYSIS; ORGANIC-CHEMISTRY; ROOM-TEMPERATURE; AROMATIC HALIDES;

D O I：

10.1021/acs.organomet.7b00208

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Detailed kinetic studies of the reaction of a model Ni-0 complex with a range of aryl electrophiles have been conducted. The reactions proceed via a fast ligand exchange pre-equilibrium, followed by oxidative addition to produce either [(NiX)-X-I(dppf)] (and biaryl) or [Ni-II(Ar)X(dppf)]; the ortho substituent of the aryl halide determines selectivity between these possibilities. A reactivity scale is presented in which a range of substrates is quantitatively ranked in order of the rate at which they undergo oxidative addition. The rate of oxidative addition is loosely correlated to conversion in prototypical cross-coupling reactions. Substrates that lead to Ni-I products in kinetic experiments conditions. produce more homocoupling products under catalytic

引用

页码：1662 / 1672

页数：11

共 84 条

[1] Oxidative addition of aryl chlorides to monoligated palladium(0): A DFT-SCRF study [J].