Substitution and redox reactions of heptarhenium cluster derivatives

The second-order rate constants for the reactivity of (Re$\sb7$C(CO)$\sb{21}$Rh(CO)$\sb2$) $\sp{2-}$ towards phosphorus donors were determined. In order to correlate the results to electronic and/or steric effects, steric profiles relating log k$\sb2$ to an intrinsic reactivity (α), an electronic parameter (β), and a steric parameter (θ) were constructed. From differences in intrinsic reactivity for phosphines and phosphites, an intermediate configuration involving a bridging carbonyl has been proposed for the reaction of (Re$\sb7$C(CO)$\sb{21}$Rh(CO)$\sb2$) $\sp{2-}$ with various phosphorus donors (PY$\sb3).$

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

2011

Author dc:creator

• Simerly, Scott W.

Contributors dc:contributor

• Shapley, John R.

• Chemistry, Inorganic

Statement dc:rights

• Copyright 1991 Simerly, Scott W.

Language dc:language

eng

Identifier

AAI9210992
(UMI)AAI9210992

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/20337