SYNTHESIS AND STRUCTURE OF HYDRIDO BIS(ETHYLENE) AND HYDRIDO DINITROGEN COMPLEXES OF RHENIUM(I) HAVING DIMETHYLPHENYLPHOSPHINE LIGANDS

mer-Hydridobis(ethylene)tris(dimethylphenylphosphine)rhenium(I) (1) and cis-hydrido(dinitrogen)tetrakis(dimethylphenylphosphine)rhenium(I) (2) have been prepared by the reaction of mer-trichlorotris(dimethylphenylphosphine)rhenium(I) with ethyllithium and n-propyllithium, respectively. X-ray structure analysis reveals that both complexes are octahedral, and in the former complex the two coordinated ethylenes occupy sites perpendicular to each other in cis positions and in the latter complex hydrido and dinitrogen ligands in cis positions. The coordinated ethylene and dinitrogen can be smoothly displaced by dihydrogen to give known trihydrido- or pentahydridorhenium complexes. Crystal data for 1: space group P1BAR, Z = 2, a = 9.285 (3) angstrom, b = 19.229 (5) angstrom, c = 9.044 (3) angstrom, alpha = 93.47 (3)-degrees, beta = 120.16 (2)-degrees, gamma = 90.23 (3)-degrees, V = 1392.5 (8) angstrom 3 , R = 0.0653, R(w) = 0.0641, based on 3959 reflections with F > 3-sigma(F). Crystal data for 2: space group P2(1)/a, Z = 4, a = 27.49 (1) angstrom, b = 10.113 (2) angstrom, c = 12.235 (6) angstrom, beta = 91.94 (4)-degrees, V = 3424 (2) angstrom 3, R = 0.0464, R(w) = 0.0533, based on 4129 reflections with F > 3-sigma(F).