温和的氧化还原互补使 [FeFe]-氢化酶模型能够激活氢气。
Mild redox complementation enables H2 activation by [FeFe]-hydrogenase models.
机构信息
School of Chemical Sciences, University of Illinois, Urbana, Illinois 61801, USA.
出版信息
J Am Chem Soc. 2011 Jun 1;133(21):8098-101. doi: 10.1021/ja201731q. Epub 2011 May 6.
Abstract
Mild oxidants such as Fe(C(5)Me(5))(2) accelerate the activation of H(2) by Fe(2)(SCH(2))(2)NBn(3)(dppv)(PMe(3)) (1), despite the fact that the ferrocenium cation is incapable of oxidizing 1. The reaction is first-order in 1 and [H(2)] but independent of the E(1/2) and concentration of the oxidant. The analogous reaction occurs with D(2) and proceeds with an inverse kinetic isotope effect of 0.75(8). The activation of H(2) is further enhanced with the tetracarbonyl Fe(2)(SCH(2))(2)NBn(4)(dppn) (2), the first crystallographically characterized model for the H(ox) state of the active site containing an amine cofactor. These studies point to rate-determining binding of H(2) followed by proton-coupled electron transfer. Relative to that by 1, the rate of H(2) activation by 2/Fc(+) is enhanced by a factor of 10(4) at 25 °C.
摘要
温和氧化剂，如Fe(C(5)Me(5))(2)，能够加速Fe(2)(SCH(2))(2)NBn(3)(dppv)(PMe(3)) (1)对 H(2)的活化，尽管 ferrocenium 阳离子本身不能氧化1。该反应对1和 H(2)呈一级反应，而与氧化剂的 E(1/2)和浓度无关。类似的反应也发生在 D(2)上，并以动力学同位素效应的倒数 0.75(8)进行。Fe(2)(SCH(2))(2)NBn(4)(dppn) (2)的存在进一步增强了 H(2)的活化，这是活性位点中含有胺辅因子的 H(ox)状态的第一个晶体结构表征模型。这些研究表明，H(2)的活化是由 H(2)的结合决定速率，然后是质子耦合电子转移。与1相比，在 25 °C 下，2/Fc(+)对 H(2)的活化速率提高了 10(4)倍。
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