University of Illinois Urbana-Champaign

Primary Photoproducts and the Mechanism of Ligand Substitution in the Photochemistry of Dinuclear Metal Carbonyls

Herrinton, Thomas Richard

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Description

Title
Primary Photoproducts and the Mechanism of Ligand Substitution in the Photochemistry of Dinuclear Metal Carbonyls
Author(s)
Herrinton, Thomas Richard
Issue Date
1984
Department of Study
Chemistry
Discipline
Chemistry
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
Chemistry, Inorganic
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).
Graduation Semester
1984
Type of Resource
text
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http://hdl.handle.net/2142/70275

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