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Herrinton, Thomas Richard 2014-12-15T23:18:18Z 2014-12-15T23:18:18Z 10000-01-01 1984 1984 Flash photolysis methods were used to investigate the photochemistry of bis(pentamethylcyclopentadienylmolybdenumtricarbonyl). The results indicate that both metal-metal bond homolysis and CO loss occur as primary photoprocesses. Transient absorbances in the visible region were observed for both primary photoproducts. The second-order rate constant for radical recombination was measured and determined to be (8.0 (+OR-) 0.6) x 10('8) M('-1) s('-1). The second-order rate constant for CO recapture was found to be (4.4 (+OR-) 0.4) x 10('3) M('-1) s('-1). In a related study, the mechanism of ligand substitution into photogenerated Mn(CO)(,5)(.) was determined to be associative. For typical phosphine and phosphite ligands the second-order rate constants varied from 10('7) to 10('9) M('-1) s('-1), with smaller, more nucleophilic ligands having the higher values. An upper limit for the dissociative rate constant was determined as 9.0 x 10('-1) s('-1). A scheme was proposed to account for the known photosubstitution chemistry of Mn(,2)(CO)(,10). Made available in DSpace on 2014-12-15T23:18:18Z (GMT). No. of bitstreams: 1 8502171.pdf: 5490336 bytes, checksum: 4c28ff91a19b96c95421b36ecc15ca34 (MD5) Previous issue date: 1984 Embargo set by: Seth Robbins for item 70441 Lift date: Forever Reason: Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs U of I Only 198 p. Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1984. http://hdl.handle.net/2142/70275 (UMI)AAI8502171 Chemistry, Inorganic Primary Photoproducts and the Mechanism of Ligand Substitution in the Photochemistry of Dinuclear Metal Carbonyls text Chemistry Chemistry University of Illinois at Urbana-Champaign Dissertation Ph.D.