Novel Intramolecular CAryl-S Bond Activation by an Electron Rich, Ring-Expanded-NHC-Rh centre: A Combined Experimental and DFT Study

被引：7

作者：

Binobaid, Abeer ^{[1
]}

Cavell, Kingsley J. ^{[1
]}

Nechaev, Mikhail S. ^{[2
,3
]}

Kariuki, Benson M. ^{[1
]}

机构：

[1] Cardiff Univ, Sch Chem, Cardiff CF10 3AT, S Glam, Wales

[2] Moscow MV Lomonosov State Univ, Dept Chem, Moscow 119991, Russia

[3] RAS, AV Topchiev Petrochem Synth Inst, Moscow 119991, Russia

来源：

AUSTRALIAN JOURNAL OF CHEMISTRY | 2011年 / 64卷 / 08期

基金：

英国工程与自然科学研究理事会;

关键词：

COMPACT EFFECTIVE POTENTIALS; EXPONENT BASIS-SETS; CARBON-SULFUR; CARBENE LIGANDS; METAL-COMPLEXES; RUTHENIUM; CLEAVAGE; CATALYSTS; IMMOBILIZATION; THIOPHENES;

D O I：

10.1071/CH11243

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The reaction of (o-MeSPh)-N-functionalized tetrahydropyrimidinium salts with KN(SiMe3)(2) and [Rh(COD)Cl](2) in THF leads to the formation of a novel dimeric Rh-III bis-carbene complex. The reaction involves the unexpected cleavage/oxidative addition of the aryl-sulfur bond to give dimeric metallated Rh-III with bridging MeS, moieties. This unusual reaction is probably a consequence of the sterically imposing structure and strong donor capacity of ring-expanded N-heterocyclic carbenes (RE-NHCs). An X-ray structure of the [(Ph,DIPP-NHC)Rh(Cl)(SMe)(2)] product complex has been obtained, and DFT studies were undertaken to gain an insight into the reaction pathway.

引用

页码：1141 / 1147

页数：7

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