Titre :

A general method for preparation of metal carbenes via solution- and polymer-based approaches.

Auteur(s) :

Gandelman, M. [Auteur]
Naing, K. M. [Auteur]
Rybtchinski, B. [Auteur]
Poverenov, E. [Auteur]
Ben-David, Y. [Auteur]
Ashkenazi, N. [Auteur]
Gauvin, Regis [Auteur]
Milstein, D. [Auteur]

Titre de la revue :

J. Am. Chem. Soc.

Nom court de la revue :

J. Am. Chem. Soc.

Pagination :

15265-72

Date de publication :

2005-10-07

ISSN :

0002-7863

Discipline(s) HAL :

Chimie

Résumé en anglais : [en]

A new general, synthetically simple, and safe method for the preparation of metal carbene complexes, which is based on diphenyl sulfonium salts as carbenoid precursors, has been developed, and its scope and applications ...
Lire la suite >A new general, synthetically simple, and safe method for the preparation of metal carbene complexes, which is based on diphenyl sulfonium salts as carbenoid precursors, has been developed, and its scope and applications were studied. In general, deprotonation of a sulfonium salt with a base results in a sulfur ylide, which, in turn, reacts with an appropriate metal precursor to give the corresponding metal carbene complex. Thus, starting from benzyldiphenylsulfonium salt, the complexes (PCX)RhCHPh (X = P, N) were prepared in quantitative yield. Syntheses of Grubbs' catalyst, (PCy3)2Cl2RuCHPh, and of Werner's carbene, [Os(CHPh)HCl(CO)(PiPr3)2], were achieved by this method. Novel trans-bisphosphine Rh and Ir carbenes, (iPr3P)2(Cl)MCHPh, which could not be prepared by other known methods, were synthesized by the sulfur ylide approach. The method is not limited to metal benzylidenes, as demonstrated by the preparation of the Ru vinyl-alkylidene, (PCy3)2Cl2RuCH−CHCH2, methoxycarbonyl-alkylidene, (PCy3)2Cl2RuCH(CO2Me), and alkylidene (PCy3)2Cl2RuCH(CH3), (PCy3)2Cl2RuCH2 compounds. The problem of recycling of starting materials as well as the issue of facile purification of the product metal carbene complex were addressed by the synthesis of a polymer-supported diarylsulfide, the carrier of the carbenoid unit in the process. Based on the sulfur ylide route, a methodology for the synthesis of metallocarbenes anchored to a polymer via the carbene ligand, using a commercial Merrifield resin, was developed.Lire moins >

Langue :

Anglais

Établissement(s) :

Université de Lille
CNRS
Centrale Lille
ENSCL
Univ. Artois

Collections :

• Unité de Catalyse et Chimie du Solide (UCCS) - UMR 8181

Date de dépôt :

2023-05-30T18:34:02Z