PHOTOCHEMISTRY OF METAL-METAL BONDED COMPOUNDS. 1. ISOLATION AND X-RAY MOLECULAR STRUCTURE ANALYSES OF ORTHOMETALATED TRIPHENYL PHOSPHITE MANGANESE CARBONYL DERIVATIVES AND REACTION MECHANISMS OF ORTHOMETALATION FROM PHOTODEGRADATION OF MANGANESE CARBONYL DERIVATIVES WITH Sn-Mn BOND.

Article abstract of DOI:10.1246/bcsj.56.87

Photochemical degradation of a series of tin-manganese bonded complexes was studied. The apparent reactivity of the tin-manganese bond toward UV irradiation is interpreted on the basis of absorption spectra of relevant complexes and available emissions from the light source. Two kinds of orthometalated products were obtained from photolysis of Me//3Sn-Mn(CO)//3 left bracket P(OPh)//3 right bracket //2 in benzene. Various kinds of experiments suggest that their photochemical reactions proceed through homolytic cleavage of the Sn-Mn bond in the initial stage and the resulting 15-electron intermediates abstract hydrogen from the triphenyl phosphite moiety. Molecular structures of the two kinds of orthometalated products, as clarified by X-ray structure analyses, are described.