Synthesis, characterization and molecular structures of the trichloro-η1-benzoyldiazenido [ReCl3{η1-NNC(O)Ph}(PPh3)2] and oxorhenium [ReOCl2(OMe)(PPh3)2] complexes derived from reactions of [ReCl2{η2-NNC(O)Ph}(PPh3)2] with a peroxide or dioxygen

The reactions of [ReCl2{eta(2)-NNC(O)Ph}(PPh3)(2)] (1) with t-BuOOH, in C6H6 or chlorinated solvents, at room temperature or with MeOH upon reflux in air lead to the trichloro-eta(1)-benzoyldiazenido [ReCl3{eta 1-NNC(O)Ph}(PPh3)(2)] (2) or the methoxy-oxo [ReOCl2(O-Me)(PPh3)(2)] (3) compound, respectively, which have been characterized by spectroscopic and FAB(+)-MS methods, elemental and single crystal X-ray diffraction analyses. They show distorted octahedral coordinaiton geometries with trans triphenylphosphine ligands, an essentially linear eta(1)-diazenido moiety in 2 and the methoxy group in 3 in trans position to the oxo ligand. (c) 2006 Elsevier B.V. All rights reserved.