| 20151688 |
Bose SK, Geetharani K, Ramkumar V, Varghese B, Ghosh S: Chemistry of vanadaboranes: synthesis, structures, and characterization of organovanadium sulfide clusters with disulfido linkage. Inorg Chem. 2010 Mar 15;49(6):2881-8.
Vanadaborane, [(CpV)(2)(B (2) H (6))(2)] (Cp = eta (5)-C (5) H (5)), 1 reacts with elemental sulfur to afford the hexasulfide cluster [(CpV)(2) S (4)(mu-eta (1)-S (2))], 2 in high yield. Compound 2 is a notable example of an organovanadium sulfide cluster in which the [V (2) S (4)] atoms define a bicapped tetrahedron framework, with one mu-eta (1)-S (2) ligand bridged the two (CpV) moieties. The sulfur atom in [V (2) S (4)] core in 2 is a four-skeletal-electron donor isoelectronic with the BH (3) unit; therefore, the replacement of boron hydride in 1 by four sulfur atoms necessitates the formation of a bicapped tetrahedron [V (2) S (4)] framework. Furthermore, this is the only reported example of a bimetallic hexasulfide cluster containing vanadium. Pyrolysis of 1 with bis-chalcogenide ligands such as Ph (2) S (2) and Bz (2) Se (2) (Bz = PhCH (2)), results in the formation of substituted vanadahexaboranes [(CpV)(2) B (4) H (12-x) L (x)], 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, (1) H, (11) B, (13) C NMR spectroscopy, and elemental analysis, and the structural types were unequivocally established by crystallographic analysis of compounds 2-5. |
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