Synthesis and catalytic evaluation of ruthenium-arene complexes generated using imidazol(in)ium-2-carboxylates and dithiocarboxylates

Lionel Delaude, Xavier Sauvage, Albert Demonceau, Johan Wouters

Research output: Contribution to journalArticlepeer-review

Abstract

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-arene 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)]PF 6 type. These stable, 18-electron species are the first examples of well-defined transition-metal complexes bearing chelating NHC·CS 2 ligands. They were characterized by various analytical techniques, and the molecular structure of [RuCl(p-cymene)(IMes·CS 2)]PF6 was determined by X-ray diffraction analysis.

Original languageEnglish
Pages (from-to)4056-4064
Number of pages9
JournalOrganometallics
Volume28
Issue number14
DOIs
Publication statusPublished - 27 Jul 2009

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