1971
DOI: 10.1021/ba-1971-0100.ch011
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The Biochemistry of N2 Fixation

Abstract: The nature of the N2ase reaction is described with respect to electron donation, energy requirement, and reduction characteristics, with particular analysis of the seven classes of substrates reducible by N2ase, a complex of a Mo-Fe and Fe protein. Chemical and physical characteristics of Fe protein and crystalline Mo-Fe protein are summarized. The two-site mechanism of electron activation and substrate complexation is further developed. Reduction may occur at a biological dinuclear site of Mo and Fe in which … Show more

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Cited by 71 publications
(20 citation statements)
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“…Propane formed in this reaction is apparently not from the subsequent reduction of propene from the 6 e − /H + reaction. This is further supported by reduction of the 4C-containing nitrile analogues, for which the reaction patterns might be more complex [47]. However, reduction of up to 4C nitriles demonstrates that substantially larger substrates than N 2 and acetylene can be accommodated by the active site of nitrogenase, even though the branched versions were not reduced [47].…”
Section: Early C-compounds and Nitrogenasementioning
confidence: 98%
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“…Propane formed in this reaction is apparently not from the subsequent reduction of propene from the 6 e − /H + reaction. This is further supported by reduction of the 4C-containing nitrile analogues, for which the reaction patterns might be more complex [47]. However, reduction of up to 4C nitriles demonstrates that substantially larger substrates than N 2 and acetylene can be accommodated by the active site of nitrogenase, even though the branched versions were not reduced [47].…”
Section: Early C-compounds and Nitrogenasementioning
confidence: 98%
“…For example, both propyne (CH 3 -C≡CH) and 1-butyne (CH 3 CH 2 -C≡CH) were found to be reduced by 2 e − /H + to the corresponding alkenes at very slow rates [47–49]. The triple bonds in propargyl alcohol and propargyl amine are also reduced by nitrogenase to yield the corresponding double-bond compounds (Table 1), which have provided valuable probes for gaining insight into where and how alkyne substrates interact with FeMo-cofactor during catalysis [50–52].…”
Section: Early C-compounds and Nitrogenasementioning
confidence: 99%
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“…The principal difficulty has been that the proteins are rapidly inactivated by oxygen. We, as well as others, have described the electron paramagnetic resonance (EPR) signals obtained from the MoFe protein at low (<30'K) temperatures, both in vivo (10) and in vitro (10)(11)(12). Because these signals appear to arise from transition metal complexes, and because it has been generally anticipated that the transition metal complexes in nitrogenase are intimately involved in the six-electron reduction of N2 to NH3 (e.g., refs.…”
mentioning
confidence: 99%
“…(10) For some of the model reactions, (5,9,11,12) binuclear activation mechanisms also have been proposed. The latter are not as firmly supported as the single metal-atom mechanisms.…”
mentioning
confidence: 99%