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

Abstract

The reaction of benzoylhydrazine with the molybdenum thiohydroxamate complex [MoO,(PhC(S)N(Me)O),] yields complex I, [MO(N,C(O)P~)(NHNHC(O)P~)(P~C(S)N(M~)~)~].O.~H~O. Cr stals of I (C30H29M~N604.5S2) are monoclinic, space group P2,/c, with a = 18.968 (6) A, b = 13.900 (4) A, c = 12.629 (3) 1, +3 = 107.90 (2)O, and Z = 4. The last blocked-matrix least-squares refinement, when the absorption correction data were used, converged with R = 0.029 and R, = 0.030. The complex contains a diazenido group and an "end-on"-bonded hydrazide( 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 5'1.361 (7) A, and Mo-N-N = 131.9 (3)O. 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)O. The 'H 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 11, [Mo(NHNC(S)Ph)(N,C(S)Ph)(PhC(S)N-(Me)O)], is formed. Complex I1 of formula C22H,9M~N50S3 crystallizes in the triclinic space group P i , with a = 11.728 (4) A, b = 11.744 (3) A, c = 11.860 (5) A, a = 60.27 (3)O, +3 = 60.57 (3)O, and y = 64.80 (3)'. The final blocked-matrix refinement converged with R = 0.024 and R, = 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) and N-N = 1.324 (6) A. Reaction of the corresponding hydroxamate complex [MoO,(PhC(O)N-(Me)O),] with thiobenzoylhydrazine led to substitution of all the initial ligands to produce the known trischelated thiobenzoyldiazene species [Mo(NHNC(S)Ph),].

Ruthenium Complexes with a Terminal Hydrazido Ligand. Synthesis, Spectroscopy, and X-ray Crystal Structure

“…The Ru−NHNPh 2 distances (average 1.911(3) Å) and Ru−N−N angles (average 141.1(3)°) are similar to the Mo−NHNPh 2 distance (1.948(5) Å) and Mo−N−N angle (140.5(4)°) in [Mo VI (NHNPh 2 )(NNPh 2 )(acac)Cl 2 ], respectively. With regard to the hydrazido(1−) ligands in 2b (see Table ), the N5, N6, C49, and C55 atoms are basically coplanar, along with the N7, N8, C61, and C67 atoms; the N−N bonds (average 1.280(4) Å) are appreciably shorter than the corresponding bond in [Mo VI (NHNPh 2 )(NNPh 2 )(acac)Cl 2 ] (1.359(6) Å) 35 but fall in the range of 1.236(19) to 1.47(2) Å, found for such bonds in the reported hydrazido(1−) complexes. −

3 ORTEP drawing of [Ru IV (TTP)(NHNPh 2 ) 2 ] ( 2b ) with atomic numbering scheme (25% probability ellipsoids). Hydrogen atoms are omitted for clarity.

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“…Currently, there are a good number of terminal hydrazido(1−) metal complexes known in the literature, all of which are monohydrazido(1−) species with metal centers spanning the groups IIIB (Sm), IVB (Ti, Zr), − VB (Ta), VIB (Mo, W), − VIIB (Tc, Re), − and VIIIB (Ir). , Strikingly, these complexes remain fully unknown for the entire subgroup of iron, ruthenium, and osmium. On the other hand, although complexes with terminal hydrazido(2−) ligands have been reported for both iron 47,48 and osmium, , respectively, none of these complexes have been isolated or even observed for ruthenium.…”

Synthesis and Characterization of Organohydrazino Complexes of Technetium, Rhenium, and Molybdenum with the {M(η1-HxNNR)(η2-HyNNR)} Core and Their Relationship to Radiolabeled Organohydrazine-Derivatized Chemotactic Peptides with Diagnostic Applications

“…The use of molybdate in the synthesis of 6 demonstrates that metal−oxo species other than those of group 7 can also be used in the syntheses. While preparation of molybdenum−hydrazido species is by no means novel, the use of vacuum-sealed glass tubes provides a useful method for the isolation of Mo−hydrazido species. These syntheses demonstrate that metal oxides [MO 4 ] - react readily with chelating hydrazine ligands in a variety of solvents to give robust complexes with a variety of metal−organohydrazine cores.…”