Hydrogen nitrogenase complexes

However, when the X-ray crystal structure of the MoFe protein was examined, it was clear that homocitrate could not directly hydrogen bond to the histidine, since the carboxylate group and imidazole are stacked parallel to each other in the crystal. Nevertheless, as noted in the previous section, studies on model complexes have suggested that homocitrate can become monodentate during nitrogenase turnover, with the molybdenum carboxylate bond breaking to open up a vacant site at molybdenum suitable for binding N2. 

Fe-hydrogenase, which usually functions in the direction of hydrogen evolution, has been known for over 30 years. This enzyme contains a highly reactive complex Fe-S center in which one of the Fe atoms is complexed with CO and CN [5], The Fe hydrogenases have extremely high turnover numbers 6,000 s 1 for C. pasteuriamm and 9,000 s 1 for Desulfovibrio spp. Note that this is a thousand times faster than the turnover number of nitrogenase ... 

The electrosynthesis of hydride complexes directly from molecular hydrogen at atmospheric pressure by reduction of Mo(II) and W(II) tertiary phosphine precursors in moderate yield has been described as also the electrosynthesis of trihydride complexes of these metals by reduction of M(IV) dihydride precursors [101,102]. Hydrogen evolution at the active site of molybdenum nitrogenases [103] is intimately linked with biological nitrogen fixation and the electrochemistry of certain well-defined mononuclear molybdenum and tungsten hydrido species has been discussed in this context [104,105]. 

In the context of alternative substrates for nitrogenases, in particular alkynes, [Equation (4.27)], model compounds are of interest in which the alkyne is coordinated side-on to vanadium. The side-on or rr coordination implies a weakening of the triple bond by TT-back-donation from vanadium-d into the tt orbitals of the ligand, and hence an activation. The activated siloxyacetylene in the complex [ClVdmpe)2 i7 -(Me3SiOC= COSiMe3)] [dmpe = bis(dimethylphosphino)ethane] is reduced by hydrogen to the respective ethene, [Equation (4.39)]. The precursor acetylene complex is formed by... 

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