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

Sengupta, D., Gangopadhyay, S., Drew, M. G. B. and Gangopadhyay, P. K. (2015) Thiohydrazide complexes of molybdenum and their relevance to reduction of dinitrogen to ammonia. Dalton Transactions, 44 (3). pp. 1323-1331. ISSN 1364-5447

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To link to this item DOI: 10.1039/c4dt01945h


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 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.

Item Type:Article
Divisions:Life Sciences > School of Chemistry, Food and Pharmacy > Department of Chemistry
ID Code:73791
Uncontrolled Keywords:Inorganic Chemistry
Publisher:Royal Society of Chemistry

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