Synthesis and Characterization of Heterobimetallic Complexes with Direct Cu-M Bonds (M = Cr, Mn, Co, Mo, Ru, W) Supported by N-Heterocyclic Carbene Ligands: A Toolkit for Catalytic Reaction Discovery

被引：56

作者：

Banerjee, Suparna ^{[1
]}

Karunananda, Malkanthi K. ^{[1
]}

Bagherzadeh, Sharareh ^{[1
]}

Jayarathne, Upul ^{[1
]}

Parmelee, Sean R. ^{[1
]}

Waldhart, Greyson W. ^{[1
]}

Mankad, Neal P. ^{[1
]}

机构：

[1] Univ Illinois, Dept Chem, Chicago, IL 60607 USA

来源：

INORGANIC CHEMISTRY | 2014年 / 53卷 / 20期

基金：

美国国家科学基金会;

关键词：

METAL-METAL BONDS; HETERONUCLEAR COORDINATION-COMPOUNDS; X-RAY CRYSTAL; CARBONYL ANIONS; MOLECULAR CALCULATIONS; CP-ASTERISK; BASIS-SETS; COBALT; COPPER; ACTIVATION;

D O I：

10.1021/ic5019778

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Building upon the precedent of catalytically active (NHC)Cu-FeCp(CO)(2) complexes, a series of (NHC)Cu-[M] complexes were synthesized via the addition of Na+[M](-) reagents to (NHC)CuCl synthons. The different [M](-) anions used span a range of 7 x 10(7) relative nucleophilicity units, allowing for controlled variation of nucleophile/electrophile pairing in the heterobimetallic species. Direct Cu-M bonds (M = Cr, Mn, Co, Mo, Ru, W) formed readily when the bulky IPr carbene was used as a support. Crystallographic characterization and computational examination of these complexes was conducted. For the smaller IMes carbene, structural isomerism was observed when using the weakest [M](-) nucleophiles, with (IMes)Cu-[M] and {(IMes)(2)Cu}{Cu[M](2)} isomers being observed in equilibrium. Collectively, the series of complexes provides a toolbox for catalytic reaction discovery with precise control of structure-function relationships.

引用

页码：11307 / 11315

页数：9

共 84 条

[51] Mechanistic Investigations of Palladium-Catalyzed Allylic Fluorination [J].