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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

Journal Article · · Inorg. Chem.; (United States)
DOI:https://doi.org/10.1021/ic00214a034· OSTI ID:6148059
The reaction of benzoylhydrazine with the molybdenum thiohydroxamate complex (MoO/sub 2/(PhC(S)N(Me)O)/sub 2/) yields complex I, (Mo(N/sub 2/C(O)Ph)(NHNHC(O)Ph)(PhC(S)N(Me)O)/sub 2/) x 0.5H/sub 2/O. Crystals of I (C/sub 30/H/sub 29/MoN/sub 6/O/sub 4.5/S/sub 2/) are monoclinic, space group P2/sub 1//c, with a = 18.968 (6) A, b = 13.900 (4) A, c = 12.629 (3) A, ..beta.. = 107.90 (2)/sup 0/, and Z = 4. 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. When the same dioxomolybdenum thiohydroxamate complex is reacted with thiobenzoylhydrazine, the complex II, (Mo(NHNC(S)Ph)(N/sub 2/C(S)Ph)(PhC(S)N(Me)O)), is formed. Complex II of formula C/sub 22/H/sub 19/MoN/sub 5/OS/sub 3/ crystallizes in the triclinic space group P1, with a = 11.728 (4) A, b = 11.744 (3) A, c = 11.860 (5) A, ..cap alpha.. = 60.27 (3)/sup 0/, ..beta.. = 60.57 (3)/sup 0/, and ..gamma.. = 64.80 (3)/sup 0/. 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. Reaction of the corresponding hydroxamate complex (MoO/sub 2/(PhC(O)N(Me)O)/sub 2/) with thiobenzoylhydrazine led to substitution of all the initial ligands to produce the known trischelated thiobenzoyldiazene species (Mo(NHNC(S)Ph/sub 3/). 42 references, 5 figures, 4 tables.
Research Organization:
Monash Univ., Clayton, Australia
OSTI ID:
6148059
Journal Information:
Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 24:20; ISSN INOCA
Country of Publication:
United States
Language:
English