Heterometallic ketenyl complex Os&O)1O(p-H) [C(O)CH2(W(CO)&p)l (la) possessing a pendant CpW(CO)3 substituent was prepared by condensation of O S ~( C O ) ~O ( N C M ~) ~ with the metal-aldehyde complex CpW(CO)&H2CHO. Pyrolysis of la in the solid state a t 185 OC afforded two heteropentametallic cluster compounds, C~~W~OS~(CO)~~(~-O)(II~-CM~) (2) and CpWOs4-(CO)12(p-O)(p3-CMe) (3), demonstrating a unique example of C-0 bond scission of a ligated ketene fragment and a cluster aggregation process. Complex 2 crystallizes in orthorhombic space group Pnma with a = 18.913(4) A, b = 16.229(3) A, c = 9.129(2) A, 2 = 4, R = 0.054, and R, = 0.055 for 2551 observed reflections. The W20s3 cluster t h a t contains 72 cluster valence electrons has a distorted square-pyramidal array of metal atoms with one Os-H-0s hydride ligand, one bridging oxo ligand associated with a W-W double bond, and a n ethylidyne ligand bridging a unique W20s triangle. Crystals of 3 are monoclinic of space group P21/n with a = 15.941(2) A, b = 19.395(4) A, c = 16.369(4) A, ,t? = 94.72(2)', 2 = 8, R = 0.050, and R, = 0.041 for 6568 observed reflections. This molecule possesses a WOS4 trigonal-bipyramidal skeleton with an oxo ligand bridging a W-Os edge and a n ethylidyne ligand capping a WOs2 face.
Condensation of the triosmium acetonitrile complex Os3(CO)~ù(NCMe) e with the sulfido complex CpW(CO)3(CHeSMe ) in refluxing THF solution produced three sulfur-containing compounds Os3(2) and CpWOs3(CO)I_~(II-CH~_)(t*-SMe) (3). Clusters 2 and 3 were products involving a 1:1 combination of starting materials and were characterized by X-ray diffraction studies. Crystals of 2 belongs to monoclinic space group P 2z/« with a=8.418(2), b=11.912(2),
Decarbonylationof triosmiummethylthiolato cluster OS3(CO)IO(J.l-H)(J.l-SMe) with Me3NO in acetonitrile solution gave cluster OS3(COMNCMe){J.l-H){J.l-SMe) (1), in which one axial CO on the non-bridged Os atom is replaced by an acetonitrile ligand. Crystal data for Z: space group P bca, a = 14.491 (I), b ;:;16.107(5), c =16.639(5) A, Z =8; R F =0.037, R, =0.033. Treatment of 2 with CpW(CO)3H in refluxing THF solution yielded two cluster compounds with formula CpWOs3(CO)1l(Il-HMIl3-SMe) (2) and CpWOsiCO)lJijJ.-HMfl-SMe) (3) as the principle products. The first possesses a spiked-triangular geometty with a triply bridging thiolato ligand and the second adopts a burterfly metal core arrangement with an edge-bridging thiolato grouping. The structure of 2 was characterized by single-crystal X-ray diffraction.Crystal data: space group P T, a = 8.865 (5), b;:; 8.959(3), c = 16.688(4) A, (X = 103.49(2),~= 93.58(3), ' Y = 113.03(4)", Z == 2, R F = 0.034, R", = 0.035.
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