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• 20605-40-7 thiobenzhydrazide 
• 97806-15-0 MoO₂(C₆H₅CON(CH₃)O)2 
• 20605-40-7 thiobenzoylhydrazine 

Relevant academic research and scientific papers

Thiohydrazide complexes of molybdenum and their relevance to reduction of dinitrogen to ammonia

Aqueous solution of sodium molybdate reacts with aromatic thiohydrazides like thiobenzhydrazide, 2-hydroxythiobenzhydrazide, furan-2-thiohydrazide and thiophen-2-thiohydrazide to form green, neutral diamagnetic 13 chelates. They were characterized by elemental analysis and spectroscopic methods. Tris(2-hydroxythiobenzhydrazido)molybdenum(vi) was crystallized from benzene and the crystal structure shows that molybdenum(vi) is hexacoordinated to three sulfur and three nitrogen atoms from three identical ligands in facile trigonal prismatic geometry. The OH group is involved in intramolecular and intermolecular hydrogen bonding. The bound ligands of tris(thiohydrazido)molybdenum(vi) undergo a redox reaction differently depending on the solvents. Two complexes of molybdenum bound to those oxidized ligands were isolated and characterized and their structures were also solved. Of them a binuclear complex, containing two MoO22+ ions, of the ligand N-2-hydroxybenzoyl-N′-2-hydroxythiobenzoylhydrazine showed some capability to catalyze the reduction of dinitrogen to ammonia by sodium borohydride. This journal is

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

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].