PHOTOLYSIS OF CpRe(CO)3 AND CpM(CO)4, WHERE M = Nb AND Ta, IN NUJOL MATRICES AND SUPERCRITICAL ETHYLENE. AN UNEXPECTED ETHYLENE POLYMERIZATION CATALYST.
T. E. Bitterwolf1, J. T. Bays1, S. Gallagher1, J. C. Linehan2, C. R. Yonker2, (1) Department of Chemistry, University of Idaho, Moscow, ID 83844, (2) Battelle Pacific Northwest Laboratory, P. O. Box 999, Richland, WA 99352.
Nujol matrix photochemical studies of CpRe(CO)3 establish the primary photochemical event to be loss of carbon monoxide to form an electron deficient species. CpM(CO)4, where M = Nb or Ta, give both CpM(CO)3 and CpM(CO)2 species upon photolysis in the Nujol matrix. Upon photolysis of these compounds in supercritical ethylene, IR bands associated with CpM(CO)n-1(ethylene) are observed as well as bands associated with CpM(CO)n-2(ethylene)2. White precipitate, formed under photochemical conditions, has been shown to be polyethylene.