Effects of metal-centre orbital control on cluster character and electron distribution between borane and hydrocarbon ligands; significance of the structures of [µ-9,10-(SMe)-8,8-(PPh₃)₂-nido-8,7-IrSB ₉H₉] and [µ-9,10-(SMe)-8-(η⁴-C₅Me₅H)- nido-8,7-RhSB₉H₉]

Abstract

In [µ-9,10-(SMe)-8-(η⁴-C₅Me₅H)- nido-8,7-RhSB₉H₉] the non-borane ligand has been found to prefer {η⁴-C₅Me₅H} rather than {η⁵-C₅Me₅} character, demonstrating factors behind (a) metallaborane core cluster control of exopolyhedral ligand-to-metal co-ordination modes, and (b) the stability of sixteen-electron transition-element centres that engender stable formally ‘low’ cluster-electron counts.

References

1. See, for example, J. D. Kennedy and B. Štíbr, in Current Topics in the Chemistry of Boron, ed. G. W. Kabalka, Royal Society of Chemistry, Cambridge, 1994, pp. 285–292 and refs. therein.
2. R. E. Williams, Inorg. Chem., 1971, 10, 210; Adv. Inorg. Chem. Radiochem., 1976, 18, 67.
3. K. Wade, Chem. Commun., 1971, 792; Adv. Inorg. Chem. Radiochem., 1976, 18, 1.
4. Y. Nishihara, K. J. Deck, M. Shang and T. P. Fehlner, J. Am. Chem. Soc., 1993, 115, 12224.
5. K. J. Adams, T. D. McGrath and A. J. Welch, Acta Crystallogr., Sect. C, 1995, 51, 401.
6. J. Holub, A. E. Wille, B. Štíbr, P. J. Carroll and L. G. Sneddon, Inorg. Chem., 1994, 33, 4920.
7. G. M. Sheldrick, Acta Crystallogr., Sect A., 1990, 46, 467.
8. G. M. Sheldrick, SHELXL 93, Program for refinement of crystal structures, University of Göttingen, 1993.
9. P. McArdle, J. Appl. Crystallogr., 1995, 28, 65.
10. S.-O. Kang, P. J. Carroll and L. G. Sneddon, Organometallics, 1988, 7, 772.
11. S.-O. Kang, P. J. Carroll and L. G. Sneddon, Inorg. Chem., 1989, 28, 96.
12. K. Nestor, X. L. R. Fontaine, N. N. Greenwood, J. D. Kennedy and M. Thornton-Pett, J. Chem. Soc., Dalton Trans., 1991, 2657.