Abstract Photolysis of [M(CO)5M′(CO)3(dab)] (M, M′ = Mn, Re; dab = 1,4-diazabuta-1,3-diene, RNCHCHNR) in 2-Me-THF leads to both homolytic and heterolytic splitting of the metalmetal bond depending on the solution temperature. In a rigid medium such as a CH4-matrix no breaking of the metalmetal bond is observed but instead formation of [M(CO)3M′(CO)3(dab)] in which compound the dab-ligand is σ
作者:Maarten W. Kokkes、Wim G.J. De Lange、Derk J. Stufkens、Ad Oskam
DOI:10.1016/0022-328x(85)88053-0
日期:1985.10
Complexes op the type (CO)5MM′(CO)3(α-diimme) (M, M′ = Mn, Re) were photolyzed in 2-Me-THF at 293 K in the absence and presence of PR3 by irradiation in the low energy M′ → α-diimine charge transfer band. In most cases the primary photoprocess appeared to be homolysis of the (M-M′) metal—metal bond. In the absence of PR3 the radicals formed react with each other to give M2(CO)10 and M′2(CO)6(α-diimine)2. It