Rhodium complexes with secondary phosphine and phosphinite ligands and the crystal structures of [(PPh2OH)2(PPh2O)Rh(μ-Cl)3Rh(PPh2OH)(PPh2O)2] and [(PPh2OH)(PPh2O)Cl(NCMe)Rh(μ-Cl)2Rh(PPh2OH)(PPh2O)Cl(NCMe)] · 2thf

RhCl3·3H2O reacts with ca six molar equivalents of PPh2H or PCy2 in EtOH solution under a N2 atmosphere and in the presence of excess NH4PF6 to yield [RhCl2(PPh2H)4]Pf6 or [RhCl2(PCy2H)4]PF6 respectivley as yellow solids. 31P{1H} NMR spectroscopy shows the presence of the trans isomer only in chloro-carbon solutions, with JRhP ca 80 Hz. Upon standing a solution of trans-[RhCl2(PPh2H)4]PF6 in a MeCH/thf mixture results in the production of yellow crystals of [(PPh2OH)(PPh2OCl(NCMeRh(μ-Cl)2Rh(rmPPh2OH)(PPH2O)Cl(NCMe)]·2thf, the structure of which shows an edge-bridge bioctahedral arrangement with View the MathML source. The NCMe ligands to the terminal Cl ligands, while the PPh2O and PPh2O− ligands are trans to the bridging Cl ligands. The crystal structure of the triply-bridged dimer [(PPh2OH)2(PPh2O)Rh(μ-Cl)3Rh(PPh2OH)(PPh2O)2] has aslo been determined, showing a face-sharing bioc-tahedral arrangement, with View the MathML source. Both dinuclear species show significant POH…OP hydrogen-bonding interactions