Kinetic Isotope Effect of the Oxidative Addition Reaction of Hydrogen to Vaska's Compound

The rates of reaction for the oxidative addition of hydrogen and deuterium gas to Ir(CO)Cl{P(C(,6)H(,5))(,3)}(,2) (Vaska's compound) have been accurately measured over the temperature range 0-50(DEGREES)C in toluene. The kinetic isotope effect, i.e., the ratio of the rate constants k(,H(,2))/k(,D(,2)), was determined over this temperature range. The kinetic isotope effect varies substantially with temperature, being inverse (k(,H(,2))/k(,D(,2)) = 0.848 at 0(DEGREES)C, exhibits a crossover point (k(,H(,2))/k(,D(,2)) = 1) at 19.94(DEGREES)C, and becomes relatively large (k(,H(,2))/k(,D(,2)) = 1.27) at 50(DEGREES)C; a plot of ln (k(,H(,2))/k(,D(,2))) vs. l/T has a slope of -661 deg('-1) and an intercept of 2.255 and is extremely linear with a correlation coefficient r = 0.999999.

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

2014

Author dc:creator

• Blumer, David James

• Chemistry, Inorganic

Language dc:language

eng

Identifier

(UMI)AAI8203406

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/67286