Understanding non-reducible N2 in the mechanism of Mo-nitrogenase.

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In my proposed mechanism of Mo-nitrogenase there are two roles for separate N2 molecules. One N2 diffuses into the reaction zone between Fe2 and Fe6 where a strategic gallery of H atoms can capture N2 to form the Fe-bound HNNH intermediate which is then progressively hydrogenated through intermediates containing HNNH2, NH and NH2 entities and then two NH3 in sequence. The second N2 can be parked in an N2-pocket about 3.2 Å from Fe2 or bind end-on at the exo coordination site of Fe2. This second N2 is outside the reaction zone, not exposed to H atom donors, and so is 'non-reducible'. Here density functional calculations using a 485+ atom model describe the thermodynamics for non-reducible N2 moving between the N2-pocket and the exo-Fe2 position, for the resting state and 19 intermediates in the mechanism. The entropy component is estimated and included. The result is that for all intermediates with ligation by H or NHx at the endo-Fe2 position the free energy for association of non-reducible N2 at exo-Fe2 is negative. There remains some uncertainty about the status of exo-Fe2-N2 during the step in which H2 exchanges with the incoming reducible N2, where at least two unbound molecules are present. At Fe2 it is evident that attainment of octahedral coordination stereochemistry dominates the binding thermodynamics for non-reducible N2. Possibilities for experimental support of these computational conclusions are discussed.