Nitrogen fixation. Part III. Electrochemical reduction of hydrazido (-NNH2) Mo and W complexes. Selective formation of NH3 under mild conditions

James Y. Becker; Shlomit Avraham (Tsarfaty)

doi:10.1016/0022-0728(90)87088-2

Nitrogen fixation. Part III. Electrochemical reduction of hydrazido (-NNH₂) Mo and W complexes. Selective formation of NH₃ under mild conditions

James Y. Becker, Shlomit Avraham (Tsarfaty)

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

26 Scopus citations

Abstract

The electrochemical reductive properties of six molybdenum and tungsten complexes were investigated by cyclic voltammetry, in THF, at Pt or glassy carbon (GC) electrodes. Each of the complexes studied contained either dinitrogen ([M(N₂)₂(dppe)₂], M = Mo, W) or hydrazido(2-) ligands ([M(X) (NNH₂)(dppe)₂]X, M = W, X = Br and M = Mo, X = Br, BF₄, or HSO₄). While none of the neutral complexes exhibited a reduction wave, each of the charged ones showed at least one reduction wave. Controlled potential electrolysis was employed for the preparative reduction of the hydrazido complexes under a N₂ atmosphere and ambient conditions, at Pt or Hg electrodes, and in the presence of inorganic acid (HBr, HBF₄, or H₂SO₄). Each of these complexes yielded NH₃ selectively, in chemical yields which ranged from 1.3% to 35.8% (per mol of complex).

Original language	English
Pages (from-to)	119-127
Number of pages	9
Journal	Journal of Electroanalytical Chemistry
Volume	280
Issue number	1
DOIs	https://doi.org/10.1016/0022-0728(90)87088-2
State	Published - 26 Feb 1990

ASJC Scopus subject areas

Analytical Chemistry
General Chemical Engineering
Electrochemistry

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title = "Nitrogen fixation. Part III. Electrochemical reduction of hydrazido (-NNH2) Mo and W complexes. Selective formation of NH3 under mild conditions",

abstract = "The electrochemical reductive properties of six molybdenum and tungsten complexes were investigated by cyclic voltammetry, in THF, at Pt or glassy carbon (GC) electrodes. Each of the complexes studied contained either dinitrogen ([M(N2)2(dppe)2], M = Mo, W) or hydrazido(2-) ligands ([M(X) (NNH2)(dppe)2]X, M = W, X = Br and M = Mo, X = Br, BF4, or HSO4). While none of the neutral complexes exhibited a reduction wave, each of the charged ones showed at least one reduction wave. Controlled potential electrolysis was employed for the preparative reduction of the hydrazido complexes under a N2 atmosphere and ambient conditions, at Pt or Hg electrodes, and in the presence of inorganic acid (HBr, HBF4, or H2SO4). Each of these complexes yielded NH3 selectively, in chemical yields which ranged from 1.3% to 35.8% (per mol of complex).",

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N2 - The electrochemical reductive properties of six molybdenum and tungsten complexes were investigated by cyclic voltammetry, in THF, at Pt or glassy carbon (GC) electrodes. Each of the complexes studied contained either dinitrogen ([M(N2)2(dppe)2], M = Mo, W) or hydrazido(2-) ligands ([M(X) (NNH2)(dppe)2]X, M = W, X = Br and M = Mo, X = Br, BF4, or HSO4). While none of the neutral complexes exhibited a reduction wave, each of the charged ones showed at least one reduction wave. Controlled potential electrolysis was employed for the preparative reduction of the hydrazido complexes under a N2 atmosphere and ambient conditions, at Pt or Hg electrodes, and in the presence of inorganic acid (HBr, HBF4, or H2SO4). Each of these complexes yielded NH3 selectively, in chemical yields which ranged from 1.3% to 35.8% (per mol of complex).

AB - The electrochemical reductive properties of six molybdenum and tungsten complexes were investigated by cyclic voltammetry, in THF, at Pt or glassy carbon (GC) electrodes. Each of the complexes studied contained either dinitrogen ([M(N2)2(dppe)2], M = Mo, W) or hydrazido(2-) ligands ([M(X) (NNH2)(dppe)2]X, M = W, X = Br and M = Mo, X = Br, BF4, or HSO4). While none of the neutral complexes exhibited a reduction wave, each of the charged ones showed at least one reduction wave. Controlled potential electrolysis was employed for the preparative reduction of the hydrazido complexes under a N2 atmosphere and ambient conditions, at Pt or Hg electrodes, and in the presence of inorganic acid (HBr, HBF4, or H2SO4). Each of these complexes yielded NH3 selectively, in chemical yields which ranged from 1.3% to 35.8% (per mol of complex).

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Nitrogen fixation. Part III. Electrochemical reduction of hydrazido (-NNH₂) Mo and W complexes. Selective formation of NH₃ under mild conditions

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