Effect of Phosphine Ligand Substitution on the Structures, Reactivities, and Ligand Rearrangements in Organotriosmium Compounds

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°).

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2015

Author dc:creator

• Hamilton, David Hughes

Contributors dc:contributor

• Joan R. Shapley

• Chemistry, Inorganic

Language dc:language

eng

Identifier

(MiAaPQ)AAI9953036

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/84455