Effect of Phosphine Ligand Substitution on the Structures, Reactivities, and Ligand Rearrangements in Organotriosmium Compounds
Hamilton, David Hughes
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https://hdl.handle.net/2142/84455
Description
Title
Effect of Phosphine Ligand Substitution on the Structures, Reactivities, and Ligand Rearrangements in Organotriosmium Compounds
Author(s)
Hamilton, David Hughes
Issue Date
1999
Doctoral Committee Chair(s)
Joan R. Shapley
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
Language
eng
Abstract
The compounds (mu-H)2Os3(CO)9L catalyze the polymerization of diazomethane. The nature of L has a strong effect on the rate of the polymerization. The rate constants for the compounds are as follows: L = CO 1.3 (2) min-1, PPh3 0.81 (12) min -1, P(p-MeOPh)3 58 (5) min-1, P(p-Tol)3 70 (6) min-1, PEt 3 0.23 (4) min-1, and PCy3 0.24 (4) min -1. The more donating ligands have slower rates of polymerization as illustrated by the fact that L = PEt3 and PCy3 have essentially the same rate constant and similar pKa's (8.69 vs. 9.70) but quite different cone angles (132° vs. 162°).
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