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DOI: 10.1039/A802446D (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1998, 2163-2168

Transition metal complexes containing the 1,2-dicarba-closo-dodecaborane-1,2-dithiolate ligand: crystal structures of [4-MeC5H4NMe]2[Pd(S2C2B10H10)I2], [NEt3H][Mo(η5-C5H5)(NO)(S2C2B10H10)I], [NBu4][Re([double bond, length half m-dash]O)(S2C2B10H10)2] and [4-MeC5H4NMe]2[{Mo([double bond, length half m-dash]O)(µ-O)(S2C2B10H10)}2]

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James D. McKinney, Hongli Chen, Thomas A. Hamor, Keith Paxton and Christopher J. Jones

Abstract

The dithiol ligand 1,2-dicarbaborane-1,2-dithiol, 1,2-(HS)2-1,2-C2B10H10 (H2cbdt), reacted with anhydrous PdI2 to form [Pd(cbdt)I2]2–, isolated as its [4-MeC5H4NMe]+ salt 1 and with [{Mo(η5-C5H5)(NO)I2}2] in the presence of NEt3 to afford the mononuclear complex [NEt3H][Mo(η5-C5H5)(NO)(cbdt)I] 2. Complete halide substitution occurred with [NBu4][Re([double bond, length half m-dash]O)Cl4] to give [NBu4][Re([double bond, length half m-dash]O)(cbdt)2] 3 and the reaction with MoCl5 in tetrahydrofuran afforded the oxo-bridged molybdenum(V) dimer [4-MeC5H4NMe]2[Mo([double bond, length half m-dash]O)(µ-O)(cbdt)}2] 4 which is diamagnetic. The salts 1–4 have been characterised by single crystal X-ray diffraction studies. In all cases only very limited conjugation appears to occur between the sulfur atoms and the carbon atoms of the carbaborane cage, C–S bond lengths averaging 1.785 Å, slightly shorter than the pure single bond value. The electrochemical properties of the new complexes were investigated but no simple reversible electron transfer processes were observed.

References

  1. U. T. Mueller-Westerhoff and B. Vance, in Comprehensive Coordination Chemistry, eds. R. D. Gillard, J. A. McCleverty and G. Wilkinson, Pergamon, Oxford, 1987, vol. 2, ch. 16.5, pp. 595–631 Search PubMed.
  2. J. A. McCleverty, Prog. Inorg. Chem., 1968, 10, 49 Search PubMed; G. N. Schrauzer, Acc. Chem. Res., 1969, 2, 72 Search PubMed.
  3. T. Jørgensen, T. K. Hansen and J. Becher, Chem. Soc. Rev., 1994, 23, 41 Search PubMed; T. K. Hansen and J. Becher, Adv. Mater., 1993, 5, 288 Search PubMed; S. R. Marder, in Inorganic Materials, eds. D. W. Bruce and D. O'Hare, Wiley, New York, 1992, ch. 3 Search PubMed; A. Kreif, Tetrahedron, 1986, 42, 1209 Search PubMed; A. F. Garito and A. J. Heeger, Acc. Chem. Res., 1974, 7, 232 Search PubMed.
  4. (a) P. Cassoux and L. Valade, in Inorganic Materials, eds. D. W. Bruce and D. O'Hare, Wiley, New York, 1992, ch. 1; Search PubMed; (b) P. Cassoux, L. Valade, M. Kobayashi, A. Kobayashi, R. A. Clark and A. E. Underhill, Coord. Chem. Rev., 1991, 110, 115 Search PubMed; (c) J. R. Ferraro and J. M. Williams, Introduction to Synthetic Electrical Conductors, Academic Press, New York, 1987, pp. 1–327 Search PubMed; (d) J. M. Williams, Adv. Inorg. Chem. Radiochem., 1983, 26, 235 Search PubMed; (e) M. Williams, A. J. Schultz, A. E. Underhill and D. M. Watkins, Extended Linear Chain Compounds, Plenum, New York, 1982, p. 73 Search PubMed; (f) J. S. Miller and A. J. Epstein, Prog. Inorg. Chem., 1976, 20, 152 Search PubMed.
  5. W. Wenseleers, E. Goovaerts, A. S. Dhindsa and A. E. Underhill, Chem. Phys. Lett., 1996, 254, 410 Search PubMed; C. A. S. Hill, A. Charlton, A. E. Underhill, K. M. A. Malik and M. B. Hursthouse, J. Chem. Soc., Dalton Trans., 1995, 587 Search PubMed; C. A. S. Hill, A. Charlton, A. E. Underhill, S. N. Oliver, S. Kershaw, R. J. Manning and B. J. Ainslie, J. Mater. Chem., 1994, 4, 1233 Search PubMed.
  6. H. D. Smith, jun., C. O. Obenland and S. Papetti, Inorg. Chem., 1966, 5, 1013 Search PubMed.
  7. H. D. Smith, jun., M. A. Robinson and S. Papetti, Inorg. Chem., 1967, 6, 1014 Search PubMed.
  8. O. Crespo, M. C. Gimeno, P. G. Jones, B. Ahrens and A. Laguna, Inorg. Chem., 1997, 36, 495 Search PubMed; O. Crespo, M. C. Gimeno, P. G. Jones and A. Laguna, J. Organomet. Chem., 1997, 547, 89 Search PubMed.
  9. (a) M. T. Ashby and J. H. Enemark, J. Am. Chem. Soc., 1986, 108, 730 Search PubMed; (b) T. A. James and J. A. McCleverty, J. Chem. Soc. A, 1971, 1068 Search PubMed; (c) T. A. James and J. A. McCleverty, J. Chem. Soc. A, 1970, 3308 Search PubMed; (d) J. A. McCleverty and D. Seddon, J. Chem. Soc., Dalton Trans., 1972, 2588 Search PubMed.
  10. J. A. McCleverty, A. S. Drane, N. A. Bailey and J. M. A. Smith, J. Chem. Soc., Dalton Trans., 1983, 91 Search PubMed; N. AlObaidi, C. J. Jones and J. A. McCleverty, Polyhedron, 1989, 8, 1033 Search PubMed.
  11. J. R. Dilworth, W. Hussain, A. J. Hutson, C. J. Jones and F. S. McQuillan, Inorg. Synth., 1996, 3, 257 Search PubMed.
  12. J. R. Dilworth, B. D. Neaves, J. Hutchinson and J. Zubieta, Inorg. Chim. Acta, 1982, 65, L223 Search PubMed; P. J. Blower, J. R. Dilworth, J. P. Hutchinson, T. Nicholson and J. Zubieta, Inorg. Chim. Acta, 1984, 90, L27 Search PubMed.
  13. W. E. Cleland, K. M. Barnhart, K. Yamanouchi, D. Collison, F. E. Mabbs, R. B. Ortega and J. H. Enemark, Inorg. Chem., 1987, 26, 1017 Search PubMed.
  14. J. D. McKinney, T. A. Hamor, C. J. Jones and K. Paxton, Polyhedron, 1997, 16, 1819 Search PubMed.
  15. F. H. Allen, O. Kennard, D. G. Watson, L. Brammer, A. G. Orpen and R. Taylor, J. Chem. Soc., Perkin Trans. 2, 1987, S1 Search PubMed.
  16. Cambridge Structural Database, Cambridge Crystallographic Data Centre, Cambridge, April 1997.
  17. R. Mattes and H. Weber, Z. Anorg. Allg. Chem., 1981, 474, 216 Search PubMed.
  18. (a) P. J. Blower, J. R. Dilworth, J. P. Hutchinson, T. Nicholson and J. Zubieta, J. Chem. Soc., Dalton Trans., 1986, 1339 Search PubMed; (b) W. Clegg, S. Boyde and C. D. Garner, Acta Crystallogr., Sect. C, 1988, 44, 172 Search PubMed.
  19. L. R. Gray, D. J. Gulliver, W. Levason and M. Webster, Acta Crystallogr., Sect. C, 1983, 39, 877 Search PubMed.
  20. M. Pfeffer, E. P. Urriolabeitia, A. de Cian and J. Fischer, J. Organomet. Chem., 1995, 494, 187 Search PubMed.
  21. J. Singh, A. K. Powell, S. E. M. Clarke and P. J. Blower, J. Chem. Soc., Chem. Commun., 1991, 1115 Search PubMed.
  22. I. G. Dance, A. G. Wedd and I. W. Boyd, Aust. J. Chem., 1978, 31, 519 Search PubMed.
  23. A. C. McDonell, T. W. Hambley, M. R. Snow and A. G. Wedd, Aust. J. Chem., 1983, 36, 253 Search PubMed; T. Nicholson, P. Lombardi and J. Zubieta, Polyhedron, 1987, 6, 1577 Search PubMed; G. Matsubayashi, T. Maikawa and M. Nakano, J. Chem. Soc., Dalton Trans., 1993, 2995 Search PubMed; R. Hubener and U. Abram, Acta Crystallogr., Sect. C, 1993, 49, 1068 Search PubMed; J. R. Dilworth, J. Hu, J. R. Miller, D. L. Hughes, J. A. Zubieta and Q. Chen, J. Chem. Soc., Dalton Trans., 1995, 3153 Search PubMed.
  24. P. L. Dahlstrom, J. R. Hyde, P. A. Vella and J. Zubieta, Inorg. Chem., 1982, 21, 927 Search PubMed; V. Sanz, T. Picher, P. Palanca, P. Gomez-Romero, E. Llopis, J. A. Ramirez, D. Beltran and A. Cervilla, ibid., 1991, 30, 3113 Search PubMed; D. Coucouvanis, S. Al-Ahmad, C. G. Kim, P. E. Mosier and J. W. Kampf, ibid., 1993, 32, 1533 Search PubMed; C. G. Kim and Coucouvanis, ibid., 1993, 32, 1881 Search PubMed; S. G. Jonasdottir, C. G. Kim and D. Coucouvanis, ibid., 1993, 32, 3591 Search PubMed.
  25. J. R. Dilworth, W. Hussain, A. J. Hutson, C. J. Jones and F. S. McQuillan, Inorg. Synth., 1996, 3, 257 Search PubMed.
  26. R. B. King, Inorg. Chem., 1967, 6, 30 Search PubMed.
  27. TEXSAN, version 1.6, Single Crystal Structure Analysis Software, Mlecular Structure Corporation, Houston, TX, 1993.
  28. G. M. Sheldrick, SHELXL 93, Program for Crystal Structure ReWnement, University of Göttingen, 1993.
  29. C. K. Johnson, ORTEP, Report ORNL-5138, Oak Ridge National Laboratory, Oak Ridge, TN, 1976.
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