Evidence for the Formation of Free 16-Electron Species Rather than Solvate Complexes in the Ultraviolet Irradiation of CpCo(CO)_2 in Liquefied Noble Gas Solvents

摘要

It is now generally well established that photodissociation of a ligand from many transition metal complexes results in the formation of a solvent-stabilized metal center within picoseconds of ligand loss, even in saturated hydrocarbon solvents. For example, Rayner and co-workers have determined that, in the gas phase, interaction between the tungsten center and hydrocarbons (RH) in (CO)_5W(RH) can be as high as 12 kcal/mol, and Yang and co-workers have established an approximately 8 kcal/mol binding energy for the first-row metal complex Cp(CO)_3Mn(n-heptane) in the liquid alkane.