[en] The ability of five imidazol(in)ium-2-carboxylates and dithiocarboxylates bearing cyclohexyl, mesityl, or 2,6-diisopropylphenyl substituents on their nitrogen atoms to act as NHC precursors for in situ catalytic applications was probed in ruthenium-promoted ring-opening metathesis and atom transfer radical polymerizations. Results obtained with 1:2 mixtures of [RuCl2(p-cymene)]2 and NHC•CO2 adducts were in line with those reported previously starting from preformed [RuCl2(p-cymene)(NHC)] complexes, whereas the NHC•CS2 zwitterions were almost completely inactive. To account for this dichotomy, the preparation of preformed ruthenium‚àíarene complexes from [RuCl2(p-cymene)]2 and NHC•CX2 inner salts was thoroughly investigated. As expected, imidazolium-2-carboxylates lost their CO2 moiety and afforded [RuCl2(p-cymene)(NHC)] complexes in high yields, whereas the NHC•CS2 betaines retained their zwitterionic nature and led to cationic complexes of the [RuCl(p-cymene)(NHC•CS2)]PF6 type. These stable, 18-electron species are the first examples of well-defined transition-metal complexes bearing chelating NHC•CS2 ligands. They were characterized by various analytical techniques, and the molecular structure of [RuCl(p-cymene)(IMes•CS2)]PF6 was determined by X-ray diffraction analysis.
Disciplines :
Chemistry
Author, co-author :
Delaude, Lionel ; Université de Liège - ULiège > Département de chimie (sciences) > Chimie macromoléculaire et catalyse organique
Sauvage, Xavier ; Université de Liège - ULiège > Département de chimie (sciences) > Chimie macromoléculaire et catalyse organique
Demonceau, Albert ; Université de Liège - ULiège > Département de chimie (sciences) > Chimie macromoléculaire et catalyse organique
Wouters, Johan
Language :
English
Title :
Synthesis and Catalytic Evaluation of Ruthenium-Arene Complexes Generated Using Imidazol(in)ium-2-carboxylates and Dithiocarboxylates
Publication date :
2009
Journal title :
Organometallics
ISSN :
0276-7333
eISSN :
1520-6041
Publisher :
American Chemical Society, Washington, United States - District of Columbia
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