Synthesis of rhodium(III) complexes with the chiral phosphine (S)-Ph2PCH2CHMeCH2OH. Crystal structure of (SRhSC)-[(eta(5)-C5Me5)RhCl(eta(2)-PPh2CH2CHMeCH2OH-P,O)]BF4

Reaction of dinuclear complex [{(eta (5)-C5Me5)RhCl}(2)(mu -Cl)(2)] with th e chiral phosphine (S)-Ph2PCH2CHMeCH2OH leads to the complex [{eta (3)-C5Me 5)RhCl2(eta (1)-PPh2CH2CHMeCH2OH-P)] (1). Complex 1 reacts with NaH and T1B F(4) affording the chiral-at-metal rhodium compounds [(eta (5)-C5Me5)RhCl(e ta (2)-PPh2CH2CHMeCH2O-P,O)] (2) and [(eta (5)-C5Me5)RhCl(eta (2)-PPh2CH2CH MeCH2OH-P,O)]BF4(3), respectively. Complex 2 has been alternatively prepare d by reaction of [{(eta (5)-C5Me5)RhCl}(2)(mu -Cl)(2)] with the sodium salt Ph2PCH2CHMeCH2ONa. Complex 2 reacts with HBF, to give 3. The reaction of 3 with an excess of NaI affords the neutral complex [(eta (5)-C5Me5)RhI2(eta (1)-PPh2CH2CHMeCH2OH-P)] (4). All the complexes have been characterised by elemental analyses and multinuclear NMR spectroscopy. The crystal structur e of complex 3 has been determined by X-ray diffraction. (C) 2001 Elsevier Science B.V. All rights reserved.