Oxidative addition of MeI to cationic Rh(I) carbonyl complexes with pyridyl bis(carbene) ligands

A series of cationic Rh(I) carbonyl complexes of the form [Rh(CO)(L)]PF6 (where L = 2,6-bis (alkylimidazol-2-ylidene)-pyridine; alkyl = Me (1a), Et (1b), CH2Ph (1c)) have been prepared by the reactions of [Rh(CO)2(OAc)]2 with diimidazolium pyridine salts in the presence of NEt3. The ν(CO) values for 1 are ca. 1982 cm−1, indicating that the N-heterocyclic carbene ligands impart high electron density on the Rh(I) centres, despite the overall cationic charge. Each of the Rh(I) complexes reacts with MeI to form two isomeric Rh(III) methyl species, and a third unidentified species. Kinetic measurements on the MeI oxidative addition reactions give second-order rate constants (MeCN, 25 °C) of 0.0927, 0.0633 and 0.0277 M−1 s−1 for 1a, 1b and 1c, respectively. Comparison of these data with those for related Rh(I) carbonyl complexes shows that 1 have remarkably high nucleophilicity for cationic species.

Graphical abstractA series of cationic Rh(I) carbonyl complexes have been prepared by the reactions of [Rh(CO)2(OAc)]2 with diimidazolium pyridine salts in the presence of NEt3. The complexes have ν(CO) values which indicate high electron density on the Rh(I) centres, and kinetic measurements on the oxidative addition of MeI show that the complexes have remarkably high nucleophilicity for cationic species.Figure optionsDownload full-size imageDownload as PowerPoint slide