Synthese von Nitrenkomplexen mit N-Trimethylsilylanilin I. Charakterisierung und Kristallstruktur von [Re(NPh)Cl3(Et2PhP)2] und [Re(NPh)Cl3(Ph3P)2] 1/2 CHC13 Synthesis of Nitrene Complexes with N -Trim ethylsilylaniline I. Characterisation and Crystal Structure of [Re(NPh)Cl3(Et2PhP)2] and [Re(NPh)Cl3(Ph3P)2] • 1/2CHC13

rra»^-mt'r-Trichlorobis(diethylphenylphosphine)phenylnitrene rhenium(V), [Re(NPh)Cl3(Et2PhP)2], has been synthesized from [ReOCl3(Et2PhP)2] and N-trimethylsilylaniline, while rrans-ttZfr-trichlorophenylnitrenebisCtriphenylphosphine) rhenium(V), [Re(NPh)Cl3(Ph3P)2] has been obtained via a novel route, from (Bu4N)[ReOCl4] and N-trimethylsilylanilin. The products were studied by mass spectrometry, IR spectroscopy and X-ray diffraction. rrafls-mer-[Re(NPh)Ch(Et-’PhP)2 ] crystallizes in the monoclinic space group P2i/n with a = 1498.5(3), b = 1068.6(1), c = 1784.0(4) pm and ß = 91.28(1)°, Z = 4. The rhenium atom exhibits a distorted octahedral coordination with the phosphine groups in trails positions, and the Cl ligands in a meridional arrangement. The R e= N -C moiety is linear with a bond angle of 169,4(5)°and a R e= N bond length o f 171.8(6) pm. [ R e ( N P h ) C h ( P h 3 P ) i ] 0.5 C H C I 3 c r y s t a l l i z e s in th e t r ic l in ic s p a c e g r o u p P i w i t h a = 1232.1 (4), b= 1431.6(5), c = 2236.6(8) pm, a = 89.19(2)°, ß = 80.50(2)°and 7 = 88.26(2)°, Z = 4. The asymmetric unit contains two symmetry independent complex molecules o f approxima­ tely 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 R e= N -C moieties have R e= N bond lengths o f 170.2(7) and 170.8(7) pm, respectively, and R e-N -C angles of 173.3(6)°and 175.0(7)°.