Stereoselective “Electrophilic” Cyclometalation of Planar-Prochiral (η6-Arene)tricarbonylchromium Complexes with Asymmetric Metal Centers: pseudo-T-4 [Cp*RhCl2]2and [Cp*IrCl2]2

The reactivity of a set of prototypical (η 6 -arene)tricarbonylchromium complexes bearing amino, oxazolyl, and pyridyl ancillary ligands versus [Cp*RhCl 2 ] 2 and [Cp*IrCl 2 ] 2 has been investigated. Successful cyclometalation reactions were achieved essentially in the presence of hydrated sodium acetate with planar-prochiral 2-phenylpyridine and 3-methyl-2-phenylpyridine complexes with yields ranging from 60% to 92%. The most salient feature of the reported reactions is their stereoselectivity, as the only diastereomers to be produced are those with the Rh- and Ir-bound chloro ligand located trans with respect to the Cr(CO) 3 . According to X-ray diffraction analyses, a relative rac -(p R, T -4- S ) configuration may be assigned to the complexes: the Cp* ligand sits unexpectedly syn with respect to the tricarbonylmetal moiety. Introduction of the Cr(CO) 3 moiety by treatment of cycloiridated 2-phenylpyridine with tricarbonyl(η 6 -naphthalene)chromium resulted in a unique diastereomer of the same relative configuration. Quantum calculations using the density functional theory were carried out on models of syn and trans -chloro isomers. Owing to strong electrostatic repulsion between the chloro ligand and the Cr(CO) 3 moiety, the syn -chloro isomers were found less stable by 7−8 kcal/mol than the trans counterparts, suggesting that cyclorhodation and cycloiridation reactions are thermodynamically controlled.