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)

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22 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 languageEnglish
Pages (from-to)119-127
Number of pages9
JournalJournal of Electroanalytical Chemistry
Volume280
Issue number1
DOIs
StatePublished - 26 Feb 1990

ASJC Scopus subject areas

  • Analytical Chemistry
  • Chemical Engineering (all)
  • Electrochemistry

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