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|Title:||Primary Photoproducts and the Mechanism of Ligand Substitution in the Photochemistry of Dinuclear Metal Carbonyls|
|Author(s):||Herrinton, Thomas Richard|
|Department / Program:||Chemistry|
|Degree Granting Institution:||University of Illinois at Urbana-Champaign|
|Abstract:||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).
Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1984.
|Date Available in IDEALS:||2014-12-15|