A Binuclear Molybdenum Complex with Two μ‐Hydrazido(3−) <i>N</i>‐Ligands

Mattes, R.; Scholand, Heinz

doi:10.1002/anie.198403821

Cited by 3 publications

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“…Some hydrazidobridged binuclear molybdenum complexes of ligands with additional S-donor atoms have also been reported. 7 In the present paper, synthesis of tris(thiohydrazido)molybdenum(VI) complexes of some aromatic thiohydrazide ligands, namely, thiobenzhydrazide, 2-hydroxythiobenzhydrazide, furan-2-thiohydrazide and thiophen-2-thiohydrazide has been described. The general scheme for the synthesis of the molybdenum complexes are shown in Scheme 1.…”

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confidence: 99%

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

et al. 2015

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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 1 : 3 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 MoO2(2+) ions, of the ligand N-2-hydroxybenzoyl-N'-2-hydroxythiobenzoylhydrazine showed some capability to catalyze the reduction of dinitrogen to ammonia by sodium borohydride.

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Section: Introductionmentioning

confidence: 99%

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

et al. 2015

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Synthesis and structural characterization of [ReO-(Et2NCS2)(NHNC(S)SMe)], a complex with a N,S-chelating hydrazido(2−) ligand

Mattes

Scholand

1986

Inorganica Chimica Acta

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Desoxo Molybdenum(IV) and Tungsten(IV) Bis(dithiolene) Complexes: Monomer−Dimer Interconversion Involving Reversible Thiol Bridge Formation

et al. 2007

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Two series of thiol-bridged dimeric desoxo molybdenum(IV) and tungsten(IV) bis(dithiolene) complexes, [Et(4)N](2)[M(IV)(2)(SR)(2)(mnt)(4)] [M = Mo, R = (1) -Ph, (2) -CH(2)Ph, (3) -CH(2)CH(3), (4) -CH(2)CH(2)OH; M = W, R = (1a) -Ph, (2a) -CH(2)Ph, (3a) -CH(2)CH(3), (4a) -CH(2)CH(2)OH] and one monomeric desoxo complex, [Et(4)N](2)[WIV(SPh)(2)(mnt)(2)] (5a) are reported. These complexes are diamagnetic, and crystal structures of each of the complex (except 5a) exhibits a dimeric {M(IV)(2)(SR)(2)} core without any metal-metal bond where each metal atom possesses hexa coordination. The M-SR distance ranges from 2.437 to 2.484 Angstrom in molybdenum complexes and from 2.418 to 2.469 Angstrom in tungsten complexes. These complexes display Mo-S(R)-Mo angles ranging from 92.84 degrees to 96.20 degrees in the case of 1-4 and W-S(R)-W angles ranging from 91.20 degrees to 96.25 degrees in the case of 1a-4a. Interestingly, both the series of Mo(IV) and W(IV) dimeric complexes respond to an unprecedented interconversion between the dimer and the corresponding hexacoordinated monomer upon change of pH. This pH-dependent interconversion establishes the fact that even the pentacoordinated Mo(IV) and W(IV) bis(dithiolene) moieties are forced to dimerize; these can easily be reverted back to the corresponding monomeric complex, reflecting the utility of dithiolene ligand in stabilizing the Mo(IV)/W(IV) moiety in synthesized complexes similar to the active sites present in native proteins.

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A Binuclear Molybdenum Complex with Two μ‐Hydrazido(3−) N‐Ligands

Abstract: than 1. We therefore examined reactions of the readily accessible dialkylchloroboranes 214] with phosphoranes 1IS1. 0 8 Angew. Chem. Int. Ed. Engl. 23 (1984) No. 5 0 Verlag Chemie GmbH, 0-6940 Weinheim, 1984 0570-0833/84/0505-0383 $ 02.50/0

Cited by 3 publications

References 6 publications

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

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

Synthesis and structural characterization of [ReO-(Et2NCS2)(NHNC(S)SMe)], a complex with a N,S-chelating hydrazido(2−) ligand

Desoxo Molybdenum(IV) and Tungsten(IV) Bis(dithiolene) Complexes: Monomer−Dimer Interconversion Involving Reversible Thiol Bridge Formation

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