COMPLEX CATALYSIS, LIV - SYNTHESIS AND CHARACTERIZATION OF ORGANORHODIUM(I) COMPLEXES WITH THE TRIDENTATE LIGAND 2,6-BIS(DIPHENYLPHOSPHANYLMETHYL)PYRIDINE [RH(PNP)R] (R = CH3, C6H5) AND THEIR REACTIVITY TOWARDETHYLENE AND PROTIC ACIDS

The organorhodium(I) complexes [Rh(PNP)R] [PNP = 2,6-bis (diphenylphos phanylmethyl)pyridine, R=CH3 (3a), C6H5 (3b)] were synthesized from [R h(PNP)(C2H4)]BF4 (1a) and LiR and characterized by P-31-, H-1-, and C- 13-NMR spectroscopy and EI mass spectrometry. In a THF solution satura ted with ethylene 3a and 3b form the five-coordinate ethylene organorh odium(I) complexes [Rh(PNP)R(C2H4)] (5a, b). The stable monohydridorho dium(III) complex [Rh(PNP)ClH(CH3CN)]SO3CF3 (7) was obtained by the re action of [Rh(PNP)Cl] with HSO3CF3 in a solution of THF/acetonitrile a nd characterized by X-ray crystallography. In a THF solution the organ orhodium(I) complexes 3a, b react upon the addition of either HSO3CF3 or HNMe3Cl with the immediate release of the respective hydrocarbon HR .