Laser Photolysis Study of the Photosubstitution in Dimanganese Decacarbonyl

Article abstract of DOI:10.1021/ja00358a010

Two primary photoprocesses in the flash photolysis of Mn(CO)10 are established with the use of a 10-ns N2 laser.One is the cleavage of the Mn-Mn bond to form ^.Mn(CO)5 radicals, and the other is the cleavage of the Mn-CO bond to form Mn(CO)9.The reactivity of Mn2(CO)9 toward ligands is found to decrease in the following order: P(n-Bu)3>>t-BuNC ca.EtCN>>CO.The substitution of CO in the ^.Mn(CO)5 radical with P(n-Bu)3 is shown to be associative.The reactivity of Mn2(CO)9 toward P(n-Bu)3 is higher than that of ^.Mn(CO)5.