Reaction of tri(2-furyl)phosphine with triosmium clusters: C-H and P-C activation to afford furyne and phosphinidene ligands

Addition of tri(2-furyl)phosphine. PFu(3), to [Os-3(CO)(10)(mu-H)(2)] at room temperature gives [HOs3(CO)(10)(PFu(3)) (mu-H)] (1), while in refluxing toluene the same reactants afford [Os-3(CO)(9)(mu(3)-PFu(2)(C4H2O))(mu-H)] (2) resulting from orthometallatation of a furyl ring. Reaction of PFu(3) with [Os-3(CO)(10-n)(NCMe)n] (n = 0, 1, 2) affords the substituted clusters [Os-3(CO)(12-n)(PFu(3))(n)] (n = 1-3) (3-5), the phosphine ligands occupying equatorial position in all cases. Heating [Os-3(CO)(11)(PFu(3))] (3) in refluxing octane gives [Os-3(CO)(9)(mu(3)-PFu)(mu(3)-eta(2)-C4H2O)] (6) which results from both carbon-hydrogen and carbon-phosphorus bond activation and contains both mu(3)-eta(2)-furyne and furylphosphinidene ligands. All new clusters have been characterized by spectroscopic methods together with single crystal X-ray diffraction for 2,3 and 6. (c) 2010 Published by Elsevier B.V.