Synthesis of phenylnitrene complexes with N-trimethylsilylaniline. III. Characterization and X-ray crystal structure of [Re(NPh)(OSiMe3)Cl(NH2Ph)(py)2][ReO4] and trans-[Re2O3Cl4(py)4]

The reaction of cis-[Re2O3Cl4(py)4] with N-trimethylsilylaniline y yields [Re(NPh)(OSiMe3)Cl(NH2Ph)(py)2][ReO4]. It crystallizes in the triclinic space group P anti 1 with a = 1085.0(6); b = 1185.2(6); c = 1331.4(6) pm; α = 65.91(5); β = 76.98(4); γ = 87.01(4) , Z = 2. In the mononuclear complex cation ReV 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) . 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 P21/n with a 895.5(3); b = 2278.4(2); c = 1259.2(3) pm; β = 102.23(1) , 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) the ReV 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. (orig.)