97751-74-1Relevant academic research and scientific papers
Reactions of oxomolybdenum(VI) hydroxamate and thiohydroxamate complexes with hydrazines. Syntheses and structures of a diazenido-hydrazido(1-) complex containing an end-on -bonded hydrazido(1-) ligand and of a diazene-diazenido(1-) derivative
FitzRoy,Frederiksen,Murray,Snow
, p. 3265 - 3270 (2008/10/08)
The reaction of benzoylhydrazine with the molybdenum thiohydroxamate complex [MoO2(PhC(S)N(Me)O)2] yields complex I, [Mo(N2C(O)Ph)(NHNHC(O)Ph)(PhC(S)N(Me)O)2]·0.5H 2O. Crystals of I (C30H29MoN6O4.5S2) are monoclinic, space group P21/c, with a = 18.968 (6) A?, b = 13.900 (4) A?, c = 12.629 (3) A?, β = 107.90 (2)°, and Z = 4. The last blocked-matrix least-squares refinement, when the absorption correction data were used, converged with R = 0.029 and Rw = 0.030. The complex contains a diazenido group and an end-on -bonded hydrazido(1-) group together with two bidentate thiohydroxamate ligands in the coordination sphere around Mo. This is the first structurally characterized end-on hydrazido(1-) complex containing the NH-NH group. Both hydrogens were located in the refinement. Selected dimensions for this group are Mo-N = 1.938 (4) A?, N-N = 1.361 (7) A?, and Mo-N-N = 131.9 (3)°. The corresponding dimensions for the diazenido group are quite different, and they are respectively 1.758 (5) A?, 1.292 (7) A?, and 168.8 (4)°. The 1H NMR spectrum of I shows coupling between the two hydrogens on the hydrazido(1-) group with doublets centered at 15.85 and 12.51 ppm. When the same dioxomolybdenum thiohydroxamate complex is reacted with thiobenzoylhydrazine, the complex II, [Mo(NHNC(S)Ph)(N2C(S)Ph)(PhC(S)N(Me)O)], is formed. Complex II of formula C22H19MoN5OS3 crystallizes in the triclinic space group P1, with a = 11.728 (4) A?, b = 11.744 (3) A?, c = 11.860 (5) A?, α = 60.27 (3)°, β = 60.57 (3)°, and γ = 64.80 (3)°. The final blocked-matrix refinement converged with R = 0.024 and Rw = 0.028. The complex possesses a distorted six-coordinate structure with three different bidentate ligands: diazene, diazenido, and thiohydroxamate. The hydrogen atom of the diazene group was found attached to the nitrogen bonded to Mo. Bond distances in the diazene group include Mo-N = 1.972 (3) A? and N-N = 1.343 (6) A? and for the diazenido group Mo-N = 1.789 (4) A? and N-N = 1.324 (6) A?. Reaction of the corresponding hydroxamate complex [MoO2(PhC(O)N(Me)O)2] with thiobenzoylhydrazine led to substitution of all the initial ligands to produce the known trischelated thiobenzoyldiazene species [Mo(NHNC(S)Ph)3].
