PHOTOCHEMICALLY INDUCED REACTIONS OF Ph2C=W(CO)5 AND Ph2C=Mn(CO)2Cp

Article abstract of DOI:10.1016/S0022-328X(00)86650-4

The photo-induced degradation of Ph2C=W(CO)5 in n-hexane solution has been investigated, and found to produce tungsten hexacarbonyl and tetraphenylethylene, as well as products of hydrogen abstraction, diphenylmethane and 1,1,2,2-tetraphenylethane.Yields of the organic products are dependent on the concentration of Ph2C=W(CO)5, the olefin being favored in more concentrated solution.Similar products and trends were found when Ph2C=W(CO)5 was thermally degraded in n-heptane.Ligand transfer of the diphenylcarbene ligand was achieved by photolyzing Ph2C=W(CO)5 in diethyl fumarate, which produced diethyl 3,3-diphenyl-1,2-cyclopropanedicarboxylate, and via a thermal reaction of Ph2C=W(CO)5 with CpMn(CO)2(THF), which produced Ph2C=Mn(CO)2Cp.Photolysis of the latter carbene complex in n-hexane produced the same organic products as those obtained from the photolysis of Ph2C=W(CO)5.