Mechanism of thermal ring closure of metal pentacarbonyl complexes, M(CO)5L (L = bidentate ligand), produced during photolysis of Group 6 hexacarbonyl complexes

The kinetics of the thermal ring-closure reactions of M(CO){sub 5}L, produced during the photolysis of M(CO){sub 6}/L for L = ethylenediamine (en) and 1,4-diisopropyl-1,4-diazabutadiene (dab), were studied as a function of (L), temperature, and pressure. The values of {Delta}S{double dagger} and {Delta}V{double dagger} are significantly negative, {minus}40 to {minus}170 J K{sup {minus}1} mol{sup {minus}1} and {minus}5.4 to {minus}13.7 cm{sup 3} mol{sup {minus}1}, respectively, for M = Cr (L = en) and M = Mo, W (L = en, dab) and support an associative ring-closure mechanism. The results demonstrate the crucial role played by the size of the metal center and the steric hindrance on L.