Synthesis of phenylnitrene complexes with n-trimethylsilylaniline .3. Characterization and X-ray crystal structure of [Re(NPh)(OSiMe(3))Cl(NH(2)Ph)(py)(2)][ReO4] and trans-[Re2O3Cl4(py)(4)]

The reaction of cis-[Re2O3Cl4(py)(4)] with N-trimethylsilylaniline yields [Re(NPh)(OSiMe(3))Cl(NH(2)Ph)(py)(2)][ReO4]. It crystallizes in the triclinic space group P (1) over bar with a = 1085.0(6); b = 1185.2(6); c = 1331.4(6)pm; alpha = 65.91(5); beta = 76.98(4); gamma = 87.01(4)degrees, Z = 2. In the mononuclear complex cation Re-V exhibits an octahedral coordination with the two pyridine molecules in cis arrangement and the trimethylsilyloxo group in trans position to the phenylnitrene ligand. The phenylnitrene ligand forms a Re=N multiple bond and an almost linear Re=N-Ph arrangement with Re2=N1 = 170.6(9) pm and Re2-N1-C10 = 176.6(8)degrees. An isomerization of the educt cis-[Re2O3Cl4(py)(4)] to the corresponding trans form was observed. The trans isomer crystallizes in the monoclinic space group P2(1)/n with a = 895.5(3); b = 2278.4(2); c = 1259.2(3) pm; beta = 102.23(1)degrees, Z = 4. In the binuclear complex with a linear O1=Re1-O2-Re2=O3 backbone and the structural parameters: Re1-O1 = 168.5(5); Re2-O3 = 168.9(5); Re1-O2 = 193.1(4); Re2-O2 = 192.4(4) pm and Re1-O2-Re2 = 178.8(2)degrees the Re-V atoms are octahedrally coordinated. The pyridine molecules and the Cl ligands of each Re atom are in trans arrangement. The i.r. and mass spectra of both products are discussed.