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Hydride-carbyne to carbene transformation in an osmium-acetate-bis(triisopropylphosphine) system: Influence of the coordination mode of the carboxylate and the reaction solvent

AuthorsBolaño, Tamara ; Castarlenas, Ricardo ; Esteruelas, Miguel A. ; Oñate, Enrique
Issue DateMar-2007
PublisherAmerican Chemical Society
CitationOrganometallics 26(8): 2037-2041 (2007)
AbstractThe bis-solvato hydride-allenylidene complex [OsH(CCCPh2)(CH3CN)2(PiPr3)2]BF4 (1) reacts with acetic acid to give the hydride-carbyne [OsH(κ2-O2CCH3)(CCHCPh2)(PiPr3)2]BF4 (2), which in 1,2-dichloroethane under reflux is stable and does not evolve into its five-coordinate carbene isomer. In acetonitrile at room temperature, complex 2 is in equilibrium with [OsH{κ1-OC(O)CH3}(CCHCPh2)(CH3CN)(PiPr3)2]BF4 (4; ΔH° = −6.4 ± 0.3 kcal·mol-1, ΔS° = −22.9 ± 1.1 eu). At 353 K, complex 4 is transformed into the carbene [Os{κ1-OC(O)CH3}(CHCHCPh2)(CH3CN)2(PiPr3)2]BF4 (5; 40%), which is obtained in high yield (88%) by reaction of [Os(CHCHCPh2)(CH3CN)3(PiPr3)2][BF4]2 with sodium acetate in 2-propanol. The hydride-carbyne to carbene transformation is analyzed by DFT calculations.
Description5 pages, 5 figures.-- Supporting Information Available: http://pubs.acs.org.
Publisher version (URL)http://dx.doi.org/10.1021/om0611655
Appears in Collections:(ICMA) Artículos
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