Synthesis and diphosphine ligand fluxionality in Os3(CO)10(bmi): Kinetic evidence for nondissociative diphosphine isomerization and X-ray crystal structure of 1,1-Os3(CO)10(bmi)
Review articleOpen access
Abstract:

AbstractThe triosmium cluster 1,2-Os3(CO)10(MeCN)2 reacts rapidly with the diphosphine ligand 2,3-bis(diphenylphosphino)-N-p-tolylmaleimide (bmi) at room temperature to give bmi-bridged cluster 1,2-Os3(CO)10(bmi) (2b) as the major product, along with the chelating isomer 1,1-Os3(CO)10(bmi) (2c) and the hydride-bridged cluster HOs3(CO)9[μ-(PPh2)CC{PPh(C6H4)}C(O)N(tolyl-p)C(O)] (3) as minor by-products. All three cluster compounds have been isolated and fully characterized in solution by IR and NMR spectroscopies (1H and 31P), and X-ray crystallography in the case of 2c. Cluster 2b is unstable and readily isomerizes to 2c in quantitative yield on mild heating. The kinetics for the conversion of 2b → 2c have been measured over the temperature range of 318–348 K in toluene solution, and based on the observed activation parameters a nondissociative isomerization process that proceeds via a transient μ2-bridged phosphine moiety is presented. Near-UV photolysis of cluster 2c at room temperature affords HOs3(CO)9[μ-(PPh2)CC{PPh(C6H4)}C(O)N(tolyl-p)C(O)] (3) with a quantum yield of 0.017. The reactivity of clusters 2b, 2c, and 3 is discussed with respect to related diphosphine-substituted Os3(CO)10(P–P) clusters prepared by our groups.

Request full text

References (0)

Cited By (0)

No reference data.
No citation data.
Advertisement
Join Copernicus Academic and get access to over 12 million papers authored by 7+ million academics.
Join for free!