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Title: 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/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 bondedmore » 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.« less

Authors:
; ; ;
Publication Date:
Research Org.:
Monash Univ., Clayton, Australia
OSTI Identifier:
6148059
Resource Type:
Journal Article
Journal Name:
Inorg. Chem.; (United States)
Additional Journal Information:
Journal Volume: 24:20
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; DIAZO COMPOUNDS; CHEMICAL PREPARATION; CRYSTAL STRUCTURE; MOLECULAR STRUCTURE; HYDRAZIDES; HYDRAZINE; CHEMICAL REACTIONS; HYDROXY COMPOUNDS; MOLYBDENUM COMPLEXES; OXYGEN COMPLEXES; SULFUR COMPLEXES; BOND ANGLE; BOND LENGTHS; CHEMICAL BONDS; COUPLING; DERIVATIZATION; EXPERIMENTAL DATA; HYDROGEN; LIGANDS; MOLYBDENUM; NITROGEN; NMR SPECTRA; COMPLEXES; DATA; DIMENSIONS; ELEMENTS; INFORMATION; LENGTH; METALS; NITROGEN COMPOUNDS; NONMETALS; NUMERICAL DATA; ORGANIC COMPOUNDS; ORGANIC NITROGEN COMPOUNDS; SPECTRA; SYNTHESIS; TRANSITION ELEMENT COMPLEXES; TRANSITION ELEMENTS; 400301* - Organic Chemistry- Chemical & Physicochemical Properties- (-1987); 360202 - Ceramics, Cermets, & Refractories- Structure & Phase Studies

Citation Formats

FitzRoy, M D, Frederiksen, J M, Murray, K S, and Snow, M R. 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. United States: N. p., 1985. Web. doi:10.1021/ic00214a034.
FitzRoy, M D, Frederiksen, J M, Murray, K S, & Snow, M R. 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. United States. https://doi.org/10.1021/ic00214a034
FitzRoy, M D, Frederiksen, J M, Murray, K S, and Snow, M R. Wed . "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". United States. https://doi.org/10.1021/ic00214a034.
@article{osti_6148059,
title = {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},
author = {FitzRoy, M D and Frederiksen, J M and Murray, K S and Snow, M R},
abstractNote = {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.},
doi = {10.1021/ic00214a034},
url = {https://www.osti.gov/biblio/6148059}, journal = {Inorg. Chem.; (United States)},
number = ,
volume = 24:20,
place = {United States},
year = {1985},
month = {9}
}