Protonation of the CoRh bond in CoRh( μ- CO)( CO) 2( μ- dppm) 2

Abstract

The electronic structure of CoRh(μ-CO)(CO) 2(μ-H 2PCH 2PH 2) 2 and CoRh(μ-H)(μ-CO)(CO) 2(μ-H 2PCH 2PH 2) 2 has been investigated by means of density functional calculations (DFT). The tetrahedral environment around the cobalt atom is the origin of the lack of direct metal-metal interaction in the former complex. In the protonated form a three-center, two-electron interaction emerges, inducing a slight lessening of the CoRh separation. The fluxionality process has also been investigated. The energy barrier for the exchange of the semibridging carbonyl with the terminal CoCO carbonyl has been computed to be 19 kcal mol −1. A second pathway involving the terminal RhCO group appears 18 kcal mol −1 above.