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-(η ⁴ -C ₅ Me ₅ H)- nido-8,7-RhSB ₉ H ₉ ] the non-borane ligand has been found to prefer {η ⁴ -C ₅ Me ₅ H} rather than {η ⁵ -C ₅ Me ₅ } 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.