Deprotonation reactions by transition-metal peroxo-complexes. Synthesis of aroylhydrazido- and aroylhydroxylamido-complexes of palladium and platinum and the crystal and molecular structures of [Pt(PPh3)2{NHNC(O)C6H4NO2-p}] and [Pt(PPh3)2{ONC(O)C6H5}]
By treating [M(PPh3)2(O2)](M = Pd or Pt) with C6H5C(O)NHOH, C6H5C(NH)NHOH, and p-RC6H4C(O)NHNH2 in ethanol, the complexes [M(PPh3)2{ONC(O)C6H5}], [Pt(PPh3)2{ONC(NH)C6H5}], and [Pt(PPh3)2{NHNC(O)C6H4R-p}](R = H, CH3, or NO2) respectively have been obtained. The reactions of [Pt(PPh3)2(O2)] with RNHNH2(R = H or C6H5) lead only to the zerovalent complex, [Pt(PPh3)3], while by treating [Pt(PPh3)2(O2)] with C6H5NHOH the known complex [Pt(PPh3)2(C6H5NO)] is obtained. Reactions of the aroylhydrazidoplatinum complexes with molecular oxygen and mineral acids are also reported. The structure of the two title complexes has been determined by X-ray diffraction. The compound [Pt(PPh3)2{ONC(O)C6H5}] is orthorhombic and crystallizes in space group Pna21 with a= 17.365(6), b= 11.218(7), and c= 18.431(8)Å, whereas the disordered [Pt(PPh3)2{NHNC(O)C6H4NO2-p}] is monoclinic and crystallizes in space group P21/m with a= 15.829(6), b= 12.269(5), c= 11.833(5)Å, and β= 93.51(3)°. Both structures have been solved by Patterson and Fourier methods, and refined to R 0.031 and 0.062 for 2 057 and 2 119 independent reflections, respectively. Both compounds, in the solid state, are essentially square-planar complexes of PtII. The differences between the two structures, which display different packing efficiency, are mainly due to the conformations of the phosphine groups, which are imposed by the chelating ligands.