Synthesis and reactivity of dithiodiphenylphosphinato-derivatives of rhodium. Crystal structure of the square-pyramidal rhodium(III) complex 2-S2PPh2)(COMe)(PPh3)>

Article abstract of DOI:10.1016/0022-328X(92)83391-T

The complexes (L2 = 1,5-cyclooctadiene (COD); L = CO) react with Na to give the mononuclear derivatives (L2 = COD, 1: L = CO, 2).Treatment of complex 2 with PPh3 affords (3).Complex 3 reacts with iodine to give a mixture of two isomers of (4).A similar reaction of 3 with methyl iodide gives the pentacoordinate rhodium(III) acyl derivative (5), which has a square-pyramidal geometry with the acyl group in the apical position, as determined by X-ray diffraction.The cationic nitrosyl derivative BF4 (6) has been prepared by reaction of complex 3 with NOBF4.Neither complex 1 nor complex 3 is a catalyst precursor for the homogeneous hydrogenation of alkenes and alkynes.