THE PHOTOCHEMISTRY OF (CO)5MNMN(CO)3(ALPHA-DIIMINE) AND XMN(CO3)(ALPHA-DIIMINE) (X=HALIDE) COMPLEXES

The Mn(CO)5 and Mn(CO)3(alpha-diimine) radicals formed by irradiation of a (CO)5MnMn(CO)3(alpha-diimine) complex undergo interesting radical coupling and electron transfer (chain) reactions. The mechanisms of these reactions are discussed and attention is paid to the character of the reactive excited state. A relationship is proposed to exist with the corresponding halide complexes XMn(CO)3(alpha-diimine) (X = Cl,Br,I) which similarly undergo homolysis of the Mn-X bond upon irradiation. Preliminary m.o. data of XMn(CO)3(bpy) and resonance Raman results obtained for BrRe(CO)3(pTol-DAB) confirm the presence of a lowest LLCT state at least for the halide complexes.