Experimental and theoretical investigations on the high-electron donor character of pyrido-annelated N-heterocyclic carbenes

Abstract

Rh(CO)2Cl(NHC) complexes of dipyrido-annelated N-heterocyclic carbenes were prepared. From the C-H coupling constant of the respective imidazolium salts and the N-C-N angle of the N-heterocyclic carbene (NHC), a weaker σ-donor character than that of typical unsaturated NHCs is expected. However, the IR stretching frequencies of their Rh(CO)2Cl complexes suggest an electrondonor character even stronger than that of saturated NHCs. We ascribe this to the extremely weak π-acceptor character of the dipyrido-annelated NHCs caused by the conjugated 14 πe- system that thus allows for an enhanced Rh-CO backbonding. This extremely low π-acceptor ability is also corroborated by the 77Se NMR chemical shift of -55.8 ppm for the respective selenourea, the lowest value ever measured for imidazole derived selenoureas. DFT-calculations of the free carbene confirm the low σ-donor character by the fact that the σ-orbital of the carbene is the HOMO-1 that lies 0.58 eV below the HOMO which is located at the π-system. Natural population analysis reveals the lowest occupation of the pπ-orbital for the saturated carbene carbon atom and the highest for the pyrido-annelated carbene. Going from the free carbene to the Rh(CO)2Cl(NHC) complexes, the increase in occupancy of the complete π-system of the carbene ligand upon coordination is lowest for the pyrido-annelated carbene and highest for the saturated carbene.