Synthesis of rhodium(III) complexes with the chiral phosphine (S)-Ph2PCH2CHMeCH2OH. Crystal structure of (SRh,SC)-[(η5-C5Me5)RhCl(η2-PPh2CH2CHMeCH2OH–P,O)]BF4

Reaction of dinuclear complex [{(η5-C5Me5)RhCl}2(μ-Cl)2] with the chiral phosphine (S)-Ph2PCH2CHMeCH2OH leads to the complex [(η5-C5Me5)RhCl2(η1-PPh2CH2CHMeCH2OH–P)] (1). Complex 1 reacts with NaH and TlBF4 affording the chiral-at-metal rhodium compounds [(η5-C5Me5)RhCl(η2-PPh2CH2CHMeCH2O–P,O)] (2) and [(η5-C5Me5)RhCl(η2-PPh2CH2CHMeCH2OH–P,O)]BF4(3), respectively. Complex 2 has been alternatively prepared by reaction of [{(η5-C5Me5)RhCl}2(μ-Cl)2] with the sodium salt Ph2PCH2CHMeCH2ONa. Complex 2 reacts with HBF4 to give 3. The reaction of 3 with an excess of NaI affords the neutral complex [(η5-C5Me5)RhI2(η1-PPh2CH2CHMeCH2OH–P)] (4). All the complexes have been characterised by elemental analyses and multinuclear NMR spectroscopy. The crystal structure of complex 3 has been determined by X-ray diffraction.