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Title:Effect of Phosphine Ligand Substitution on the Structures, Reactivities, and Ligand Rearrangements in Organotriosmium Compounds
Author(s):Hamilton, David Hughes
Doctoral Committee Chair(s):Joan R. Shapley
Department / Program:Chemistry
Discipline:Chemistry
Degree Granting Institution:University of Illinois at Urbana-Champaign
Degree:Ph.D.
Genre:Dissertation
Subject(s):Chemistry, Inorganic
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°).
Issue Date:1999
Type:Text
Language:English
Description:179 p.
Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1999.
URI:http://hdl.handle.net/2142/84455
Other Identifier(s):(MiAaPQ)AAI9953036
Date Available in IDEALS:2015-09-25
Date Deposited:1999


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