SYNTHESIS OF NITRENE COMPLEXES WITH N-TRIMETHYLSILYLANILINE .1. CHARACTERIZATION AND CRYSTAL-STRUCTURE OF [RE(NPH)CL-3(ET(2)PHP)(2)] AND [RE(NPH)CL-3(PH(3)P)(2)].1/2CHCL(3)

trans-mer-Trichlorobis(diethylphenylphosphine)phenylnitrene rhenium(V),[Re(NPh)Cl-3(Et(2)PhP)(2)] has been synthesized from [ReOCl3(Et(2)PhP)(2)] and N-trimethylsilylaniline, while trans-mer-trichlorophenylnitrenebis(triphenylphosphine) rhenium(V), [Re(NPh)Cl-3(Ph(3)P)(2)] has been obtained via a novel route, from (Bu(4)N)[ReOCl4] and N-trimethylsilylanilin. The products were studied by mass spectrometry, IR spectroscopy and X-ray diffraction. trans-mer-[Re(NPh)Cl-3(Et(2)PhP)(2)] crystallizes in the monoclinic space group P2(1)/n with a = 1498.5(3), b = 1068.6(1), c = 1784.0(4) pm and beta = 91.28(1)degrees, Z = 4. The rhenium atom exhibits a distorted octahedral coordination with the phosphine groups in trans positions, and the Cl ligands in a meridional arrangement. The Re=N-C moiety is linear with a bond angle of 169,4(5)degrees and a Re=N bond length of 171.8(6) pm. [Re(NPh)Cl-3(Ph(3)P)(2)]. O.5CHCl(3) crystallizes in the triclinic space group P ($) over bar 1 with a 1232.1(4), b = 1431.6(5), c = 2236.6(8) pm, alpha = 89.19(2)degrees, beta = 80.50(2)degrees and gamma = 85.26(2)degrees, Z = 4. The asymmetric unit contains two symmetry independent complex molecules of approximately the same structure, with Cl atoms meridionally arranged and the phosphine groups in trans positions. The coordination geometry is a distorted octahedron. The almost linear Re=N-C moieties have Re=N bond lengths of 170.2(7) and 170.8(7) pm, respectively, and Re-N-C angles of 173.3(6)degrees and 175.0(7)degrees.