1. Characterization and structures of intermediates in the reactivity of CpWOs3(CO)11(μ3-CTol) towards dihydrogen and water

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author J. T. Park, J.-H. Chung, H. Song, K. Lee, J.-H. Lee, J.-R. Park, and I.-H. Suh
journal J. Organomet. Chem., 1996, 526, 215
link http://www.sciencedirect.com/science/art...8X9606562X
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Initial decarbonylation of CpWos3(Co)11(μ3-CTol) (1: Cp = η5-C5H5, Tol = p-C6H4Mc) with the Me3NO/MeCN followed by reaction with dihydrogen and water produces a dihydrido comlex CpWOs3(CO)10(μ3-CTol)(μ-H)2 (2), a ‘butterfly’ cluster with a 60 valence electron (VE), and an oxo comlex CpWOs3(CO)10(μ-O)(μ3-CTol) (4) respectively. Complex 2 reacts either with carbon monoxide to produce the starting alkylidyne complex 1 by reductive elimination of dihydrogen or with PPh3 to afford a 62 VE ‘butterfly’ complex. CpWOs3(CO)10(PPh3)(μ3-CTol)(μ-H)2 (6). Thermolysis of 2 in the presence of water gives a hydrido oxo alkylidene complex, syn-CpWOs3(CO)9(μ-O)(μ-CHTol)(μ-H) (3a), in which the totyl substituent on the alkylidene carbon is oriented syn to the μ-oxo ligand. Thermolysis of 4 at 110°C induces decarbonylation to give a tetrahedral alkylidyne complex CpWOs3(CO)9(μ-O)(μ3-CTol) (5), which is reversibly converted back to 4 upon exposure to carbon monoxide. Complex 5 reacts with dihydrogen to afford a mixture of two isomeric hydrido oxo alkylidene complexes, antiCpWOs3(CO)9(μ-O)(μ-CHToL)(μ-H) (3b,c). The syn-isomer 3a is also produced from a mixture of 3b and 3c by thermolysis in boiling toluene. Compounds 2, 3a,b,c, 4, 5, and 6 haven been isolated as crystalline solids and characterized by spectroscopic (IR, MS, 1H and 13CMMR) and analytical data. The structures of 2 and 6 have been determined by single crystal X-ray diffraction studies. Compound 2 crystallizes in the orthorhombic space group P212121 with unit cell parameters a = 14.18(1), b = 28.46(1), Full-size image (<1 K), Full-size image (<1 K) and Z = 8. Compound 6 crystallizes in the monoclinic space group P21/n with unit cell parameters a= 19.298(2), Full-size image (<1 K) and Z= 4. Diffraction data were collected on a CAD4 diffractometer, and structures were refined to R = 0.0957 and 0.0510 for 2 and 6 respectively. Both 2 and 6 are based upon a ‘butterfly’ WOs3 metal core with a respective dihedral angle of 114.3(2)° and 113.6(4)° between the W-Os(2)-Os(1) and W-Os(2)-Os(3) planes. Each molecule consists of three Os(CO)3 units and a CpW(CO) fragment, except that the Os(1) center in 6 is additionally coordinated with PPh3. The μ3-alkylidyne caps unsymmetrically the respective W-Os(2)-Os(3) face of both complexes.

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