Addition and elimination of hydrogen and ligand substitution on triosmium clusters. Kinetics and mechanism
作者:Lynn M. Bavaro、Jerome B. Keister
DOI:10.1016/0022-328x(85)80090-5
日期:1985.6
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.
Thermolysis of the substituted triosmium cluster Os3(CO)11(AsPh3) in refluxing nonane gave four major products: Os3(μ3-AsPh)(μ3,η2-C6H4)(CO)9, Os3(μ-H)(μ-AsPh2)(μ3,η2-C6H4)(CO)9, Os3(μ-AsPh2)2(μ3,η2-C6H4)(CO)7 and Os3(μ3-AsPh)(μ3,η2-C6H4)(CO)8(AsPh3). All the new clusters have been characterised by spectroscopy and single-crystal X-raycrystallographic studies.
热解的取代triosmium簇锇3(CO)11(ASPH 3)在回流的壬烷,得到四种主要产品:O的3(μ 3 -ASPh)(μ 3,η 2 -C 6 H ^ 4)(CO)9,锇3(μ-H)(μ-ASPH 2)(μ 3,η 2 -C 6 H ^ 4)(CO)9,锇3(μ-ASPH 2)2(μ 3,η 2 -C 6 H ^ 4) (CO)7和Os 3(μ 3 -ASPh)(μ 3,η 2 -C 6 H ^ 4)(CO)8(ASPH 3)。所有新的团簇均已通过光谱学和单晶X射线晶体学研究进行了表征。