pubs.acs.org/IC Published on Web 02/12/2010 r 2010 American Chemical Society Inorg. Chem. 2010, 49, 2881–2888 2881 DOI: 10.1021/ic9023597 Chemistry of Vanadaboranes: Synthesis, Structures, and Characterization of Organovanadium Sulfide Clusters with Disulfido Linkage Shubhankar Kumar Bose, † K. Geetharani, † V. Ramkumar, † Babu Varghese, ‡ and Sundargopal Ghosh* ,† † Department of Chemistry, Indian Institute of Technology Madras, Chennai 600 036, India, and ‡ Sophisticated Analytical Instruments Facility, Indian Institute of Technology Madras, Chennai 600 036, India Received November 29, 2009 Vanadaborane, [(CpV) 2 (B 2 H 6 ) 2 ](Cp = η 5 -C 5 H 5 ), 1 reacts with elemental sulfur to afford the hexasulfide cluster [(CpV) 2 S 4 (μ-η 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 μ-η 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. Introduction The chemistry of transition metal complexes with chalcogen ligands is of immense importance to a wide range of che- mical, industrial, and biological systems. 1-12 These complexes have also been used as molecular precursors for the pre- paration of advanced materials 13 and industrial catalysis. 14 Extensive studies have documented the reactivity associated with the chalcogenide ligands in discrete metal sulfido com- plexes. 15-21 For example, compounds of the type [(RC 5 - H 4 ) 2 TiS 5 ] (R=H, CH 3 ), [(RC 5 H 4 ) 2 V 2 S 4 ] (R=H, CH 3 , (CH 3 ) 2 CH), [(Cp 2 Cr 2 S(S-t-Bu) 2 ], [(CH 3 R 4 C 5 ) 2 Mo 2 S 4 ] (R= CH 3 , H) and [Fe 2 (S 2 )(CO) 6 ] have been employed for organic *To whom correspondence should be addressed. E-mail: sghosh@ iitm.ac.in. (1) Murphy, D. W.; Christian, P. A. Science (Washington, D.C.) 1979, 205, 651. (2) (a) King, R. B.; Treichel, P. M.; Stone, F. G. A. J. Am. Chem. Soc. 1961, 83, 3600. (b) Holm, R. H.; King, R. B.; Stone, F. G. A. Inorg. Chem. 1963, 2, 219. (c) King, R. B. J. Am. Chem. Soc. 1962, 84, 2460. (3) (a) Hullinger, F. Struct. Bonding (Berlin) 1968, 4, 83. (b) Rouxel, J.; Brec, R. Annu. Rev. Mater. Sci. 1986, 16, 137. (4) (a) Rankel, L. A.; Rollman, L. D. Fuel 1983, 62, 44. (b) Galiasso, R.; Blanco, R.; Gonzalez, C.; Quinteros, N. Fuel 1983, 62, 817. (c) Silbernagel, B. G. J. Catal. 1979, 56, 315. (d) Reynolds, J. G.; Biggs, W. R.; Fetzer, J. C. Liq. Fuels Technol. 1985, 3, 423. (5) (a) Robson, R. L.; Eady, R. R.; Richardson, T. H.; Miller, R. W.; Hawkins, M.; Postgate, J. R. Nature (London) 1986, 322, 388. (b) Hales, B. J.; Case, E. E.; Morningstar, J. E.; Dzeda, M. F.; Mauterer, L. A. Biochemistry 1986, 25, 7251. (6) Arber, J. M.; Dobson, B. R.; Eady, R. R.; Stevens, P.; Hasnain, S. S.; Garner, C. D.; Smith, B. E. Nature (London) 1987, 325, 372. (7) (a) Herbst, K.; Monari, M.; Brorson, M. Inorg. Chem. 2002, 41, 1336. (b) Burgess, B. K.; Lowe, D. J. Chem. Rev. 1996, 96, 2983. (8) Riaz, U.; Curnow, O. J.; Curtis, M. D. J. Am. Chem. Soc. 1994, 116, 4357. (9) Takei, I.; Suzuki, K.; Enta, Y.; Dohki, K.; Suzuki, T.; Mizobe, Y.; Hidai, M. Organometallics 2003, 22, 1790. (10) Wakabayashi, T.; Ishii, Y.; Murata, T.; Mizobe, Y.; Hidai, M. Tetrahedron Lett. 1995, 36, 5585. (11) Murata, T.; Mizobe, Y.; Gao, H.; Ishii, Y.; Wakabayashi, T.; Nakano, F.; Tanase, T.; Yano, S.; Hidai, M.; Echizen, I.; Nanikawa, H.; Motomura, S. J. Am. Chem. Soc. 1994, 116, 3389. (12) Takei, L.; Dohki, K.; Kobayashi, K.; Suzuki, T.; Hidai, M. Inorg. Chem. 2005, 44, 3768. (13) (a) Whittingham, M. S. Prog. Solid State Chem. 1978, 12, 41. (b) Franzen, H. F. Prog. Solid State Chem. 1978, 12, 1. (c) Rao, C. N.; Pisharody, K. P. R. Prog. Solid State Chem. 1976, 10, 207. (14) (a) Pan, W.-H.; Johnston, D. C.; McKenna, S. T.; Chianelli, R. R.; Halbert, T. R.; Hutchings, L. L.; Stiefel, E. I. Inorg. Chim. Acta 1985, 97, L17. (b) McCleverty, J. A.; Spencer, N.; Bailey, N. A.; Shackleton, S. L. J. Chem. Soc., Dalton Trans. 1980, 1939. (c) Rakowski DuBois, M.; VanDerveer, M. C.; DuBois, D. L.; Haltiwanger, R. C.; Miller, W. K. J. Am. Chem. Soc. 1980, 102, 7456. (15) (a) Adams, R. D.; Wang, S. Organometallics 1985, 4, 1902. (b) Rajan, O. A.; McKenna, M.; Noordik, J.; Haltiwanger, R. C.; Rakowski DuBois, M. Organometallics 1984, 3, 831. (c) Bolinger, C. M.; Rauchfuss, T. B.; Rheingold, A. L. J. Am. Chem. Soc. 1983, 103, 6321. (d) Bolinger, C. M.; Rauchfuss, T. B.; Wilson, S. R. J. Am. Chem. Soc. 1984, 106, 7800. (16) Halbert, T. R.; Pan, W.-H.; Stiefel, E. I. J. Am. Chem. Soc. 1983, 105, 5476. (17) Rauchfuss, T. B.; Rodgers, D. P. S.; Wilson, S. R. J. Am. Chem. Soc. 1986, 108, 3114. (18) Bolinger, C. M.; Rauchfuss, T. B. Organometallics 1982, 1, 1551. (19) Bolinger, C. M.; Rauchfuss, T. B.; Wilson, S. R. J. Am. Chem. Soc. 1982, 104, 7313. (20) (a) Mathur, P.; Singh, A. K.; Mohanty, J. R.; Chatterjee, S.; Mobin, S. M. Organometallics 2008, 27, 5094. (b) Mathur, P.; Manimaran, B.; Hossain, Md. M.; Shanbag, R.; Murthy, J.; Saranathan, I. S.; Satyanarayana, C. V. V.; Bhadbhade, M. M. J. Organomet. Chem. 1995, 490, 173. (c) Adams, R. D.; Babin, J. E.; Mathur, P.; Natarajan, K.; Wang, J. G. Inorg. Chem. 1989, 28, 1440.