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• W2095484449 endingPage "5439" @default.
• W2095484449 startingPage "5431" @default.
• W2095484449 abstract "Substitution of the MeCN ligands in the activated cluster Os3(CO)10(MeCN)2 (1) by the unsaturated diphosphine ligand (Z)-Ph2PCHCHPPh2 proceeds rapidly at room temperature to furnish the ligand-bridged cluster 1,2-Os3(CO)10[(Z)-Ph2PCHCHPPh2] (2b). Heating 2b leads to the formation of the thermodynamically more stable chelating isomer 1,1-Os3(CO)10[(Z)-Ph2PCHCHPPh2] (2c). The molecular structure of each isomer of 2 has been crystallographically determined, and the 31P NMR data have been recorded. The kinetics for the ligand isomerization have been investigated by UV−vis and 31P NMR spectroscopy in toluene solution over the temperature range of 358−383 K. The reversible nature of the diphosphine isomerization is confirmed by 31P NMR measurements, and reported within are the forward (k1) and reverse (k-1) first-order rate constants for the bridge-to-chelate rearrangement. On the basis of the activation parameters and lack of CO inhibition on the reaction rate, a nondissociative, intramolecular mechanism involving the migration of one P group from an adjacent osmium center to the other P-substituted osmium center via a μ2-bridged phosphine species is presented." @default.
• W2095484449 created "2016-06-24" @default.
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• W2095484449 date "2005-09-29" @default.
• W2095484449 modified "2023-10-16" @default.
• W2095484449 title "Reversible Isomerization of a Diphosphine Ligand about a Triosmium Cluster: Synthesis, Kinetics, and X-ray Structures for the Bridging and Chelating Isomers of Os₃(CO)₁₀[(<i>Z</i>)-Ph₂PCHCHPPh₂]" @default.
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• W2095484449 doi "https://doi.org/10.1021/om0505413" @default.
• W2095484449 hasPublicationYear "2005" @default.
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