Oxidative Addition of the C−S Bond of Thiophene to the (C5Me5)Rh(PMe3) Fragment: A Theoretical Study Revisited

Density functional theory (DFT) calculations on the C−S bond activation reaction of thiophene with the [(C 5 Me 5 )Rh(PMe 3 )] fragment have been reinvestigated, giving two new isomeric C−S bond activation transition states, in which the coordinated thiophene molecule tilts toward either the C 5 Me 5 ligand or the PMe 3 ligand. Through intrinsic reaction coordinate (IRC) calculations, these transition states were found to connect the oxidative addition product with two isomeric η 2 -C,S coordinated intermediates. These latter intermediates in turn connected to two isomeric η 1 -S and η 2 -C,C coordinated species. The energetics and mechanistic details are described.