30173-89-8Relevant academic research and scientific papers
Substitution Kinetics of and
Dahlinger, Karl,Poe, Anthony J.,Sayal, Pardeep K.,Sekhar, Vasu C.
, p. 2145 - 2148 (2007/10/02)
The kinetics of reactions of and with P- or As-donor ligands in p-xylene or toluene have been studied and shown to be characteristic of reversible dissociative processes.In both cases MeCN is ca. 10 times more nucleophilic towards the reactive intermediate than is PPh3.Activation parameters confirm the weakness of the Os-NCMe bonds and suggest that loss of the first MeCN from may be a concerted process in which a 'sideways on' bridging CO replaces the leaving MeCN.The strength of bridge bonding can be estimated to be >= 30kJmol-1.
ADDITION AND ELIMINATION OF HYDROGEN AND LIGAND SUBSTITUTION ON TRIOSMIUM CLUSTERS. KINETICS AND MECHANISM.
Bavaro, Lynn M.,Keister, Jerome B.
, p. 357 - 368 (2007/10/02)
The kinetics of the reversible reaction HOs3(μ-COMe)(CO)10 + H2 H3Os3(μ3-COMe)(CO)9 + CO has been investigated.The reaction of HOs3(μ-COMe)(CO)10 with hydrogen involves dissociation of a CO ligand prior to the rate-determining step, which is proposed to be the oxidative addition of molecular hydrogen.The reaction of H3Os3(μ-COMe)(CO)9 with CO involves rate-limiting hydrogen loss.The equilibrium constant and the competition ratio for hydrogen and CO for the unsaturated intermediate were determined.The mechanism of substitution by AsPh3 on HOs3(μ-COMe)(CO)10 also involves a CO dissociative mechanism.Based upon relative rate constants for CO, AsPh3, and hydrogen addition to HOs3(COMe)(CO)9, CO dissociation and hydrogen addition are proposed to occur at different metal sites.
