Expanding the Concepts Trans Influence and Back-Donation: Hybrid and Side Donations in [Cp*MIII(L)XY] (M = Rh, Ir) Complexes with CO, CN-, and CNR Ligands. A Window to Cis Influence.

Analysis of the bonding contributions in molecules [MIIICp*(L)XY] (M = Rh, Ir; Cp* = C5Me5; L = CO, CN-, CNR) has uncovered a rich variety of types of interaction that seem to have escaped detection so far, in spite of the continuous popularity of cyclopentadienyl transition-metal complexes since the 1970s. At variance with the M-C≡O bond in square-planar systems, which shows typical metal-to-CO π-back-donation, the nonorthogonal arrangement of the Cp* plane and Rh-C≡O fragment and the pseudooctahedral geometry lead to the observation of many direct lateral donations from other ligands that do not involve the metal orbitals, and we name side donations, for instance, Cp* → π*(CO), Cl → π*(CO), and F → π*(CO). Hybrid donations partially involving the metal, M-Caryl → π*(CO), are also observed. The summation of multiple contributions other than back-donation can easily account for about 20% of the electron donation to the π*(C≡O) orbitals.