Vanadaborane, [(CpV)2(B2H6)2] (Cp = η5-C5H5), 1 reacts with elemental sulfur to afford the hexasulflde cluster [(CpV)2S4(μ- η1-S2)], 2 In high yield. Compound 2 is a notable example of an organovanadium sulfide cluster In which the [V2S 4] atoms define a bicapped tetrahedron framework, with μ-η1-S2 ligand bridged the two (CpV) moieties. The sulfur atom In [V2S4] core in 2 Is a four-skeletal- electron donor isoelectronlc with the BH3 unit; therefore, the replacement of boron hydride in 1 by four sulfur atoms necessitates the formation of a bicapped tetrahedron [V2S4] framework. Furthermore, this Is the only reported example of a bimetallic hexasulflde cluster containing vanadium. Pyrolysls of 1 with bis-chalcogenide ligands such as Ph2S2 and Bz2Se2 (Bz = PhCH 2), results In the formation of substituted vanadahexaboranes [(CpV)2B4H12-xLx], 3-5 (3: L = SPh: x= 3; 4: L = SPh, x= 2; 5: L = SeBz: x= 1) in modest yield. All these new compounds have been characterized by mass, 1H, 11B, 13C NMR spectroscopy, and elemental analysis, and the structural types were unequivocally established by crystallographic analysis of compounds 2-5. © 2010 American Chemical Society.