58 - 1258 J CHEM S OC CHEM COMMUN 1987 The First Example of...

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1258 J. CHEM. SOC., CHEM. COMMUN., 1987 The First Example of a Niobium-Sulphide-Thiolate Cluster: Metal-Metal Bonding and p4-Sulphide Groups in Tetranuclear [Nb4S2(SPh)1214- Jeffrey L. Seela, John C. Huffman, and George Christou" Department of Chemistry and the Molecular Structure Center, Indiana University, Bloomington, IN 47405, U.S.A. Reaction of Nb2C16(Me2S)3 with of excess of LiSPh-THF (THF = tetrahydrofuran) leads to formation of Li4[Nb4S2(SPh)12].4THF: the crystal structure shows the tetra-anion to contain a metal-metal bonded Nb4 square with a p4-S*- atom both above and below the metal plane. Continuing interest in early transition metal sulphide com- pounds stems from their relevance to a variety of areas, including heterogeneous catalysis,' development of novel electrode materials,2 and the occurrence of M-S linkages within biological systems.3 Most effort to date has been concentrated on Mo (and W) chemistry,4 but some recent interest in Zr/S/SRS and V/S/SR6 chemistry has been reported. Our own interest in the latter has now been extended to niobium and we have investigated the reaction of the double-bonded complex Nb2C16(Me2S)37 with PhS- , seeking a metathesis reaction to yield a dinuclear Nb/SPh species which might, on reaction with elemental S or S2-, lead to higher nuclearity Nb/S/SPh clusters. We herein report that this reaction instead leads directly to a tetranuclear sulphide- bridged species, and describe the structure of the interesting [Nb4S2(SPh)12]4- cluster. A solution of Nb2C16(Me2S)3 (3.4 mmol) in toluene (75 ml) was added over 10 min to a stirred slurry of LiSPh-THF (THF = tetrahydrofuran) (21.3 (125 ml). The white solid slowly dissolved to yield an intensely coloured red-brown solution. After an additional 2 h stirring, the reaction mixture was filtered, and hexanes (200 ml) added to precipitate a dark brown powder. The product was collected by filtration, washed copiously with hexanes, and dried in
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J. CHEM. SOC., CHEM. COMMUN., 1987 1259 Figure 1. ORTEP projection at the 20% probability level of the anion of complex (1). Primed and unprimed numbers are related by the inversion centre. Selected distances (A) and angles (O): Nb(1)-Nb(2), 2.8261(22); Nb(1)-Nb(2’), 2.8291(22); Nb(1)-S(3), 2.462(4); Nb(1)-S(3’), 2.516(4); Nb(2)-S(3), 2.513(4); Nb(2)-S(3‘), 2.515(4); Nb( l)-S(4), 2.534(5); Nb(2)-S(11), 2.650(4); Nb( l)-S(18,25,32’,39’), 2.641(4), 2.598(4), 2.624(4),
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58 - 1258 J CHEM S OC CHEM COMMUN 1987 The First Example of...

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