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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Mechanistic studies on proton transfer in a [FeFe] hydrogenase mimic complex
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Mechanistic studies on proton transfer in a [FeFe] hydrogenase mimic complex

机译：[FeFe]氢化酶模拟复合物中质子转移的机理研究

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摘要

Four different pathways for deprotonation of [(μ-pdt){Fe(CO)_3}{Fe(CO)(κ~2-Me_2PCH_2N(Me) CH2PMe_2)}] (pdt = propane-1,3-dithiolate) [1H_μ]~(1+) were examined, including (1) the "Direct" deprotonation; (2) the "Indirect" deprotonation via the pendant amine N; (3) the "Indirect" deprotonation via the distal metal Fe; and (4) the "Indirect" deprotonation via the dithiolate S. Only deprotonation of the "Indirect" pathway via the pendant amine N is feasible at room temperature. The most favorable migration destination for the bridging hydride in [1H_μ]~(1+) is the pendant amine N (activation energy barrier 16.1 kcal mol~(-1)). Migrations to the other two possible sites including the distal metal Fe (34.6 kcal mol~(-1)) and the S in the dithiolate group (41.5 kcal mol~(-1)) were hindered by high proton shuttling barriers. Once the migration barriers of those three "Indirect" pathways are overcome, the following deprotonations from all three positions including the distal atom Fe, the dithiolate S and the pendant amine N, are all feasible. The results also demonstrate a large difference for deprotonation of the hydride from the terminal and bridging sites. The low energy of the virtual orbital associated with the antibonding M-H interaction of [1H_(Fe)]~(1+) implies the high activity for the interaction with aniline.
机译：[（μ-pdt）{Fe（CO）_3} {Fe（CO）（κ〜2-Me_2PCH_2N（Me）CH2PMe_2）}]的四个不同质子化途径（pdt =丙烷-1,3-二硫代丙烷）[1H_μ ]〜（1+）被检查，包括（1）“直接”去质子; （2）通过侧链胺N的“间接”去质子; （3）通过远端金属Fe的“间接”去质子; （4）经由二硫醇盐S的“间接”去质子化。仅在室温下经由悬垂胺N对“间接”途径的去质子化是可行的。在[1H_μ]〜（1+）中，桥接氢化物最有利的迁移目的地是侧基胺N（活化能垒16.1 kcal mol〜（-1））。高质子穿梭势垒阻碍了向远端金属Fe（34.6 kcal mol〜（-1））和S的二硫酸酯基团（41.5 kcal mol〜（-1））迁移到其他两个可能的位置。一旦克服了这三个“间接”途径的迁移障碍，从包括远端原子Fe，二硫醇盐S和侧基胺N在内的所有三个位置进行以下脱质子反应都是可行的。结果还证明了氢化物从末端和桥连位置去质子化的巨大差异。与[1H_（Fe）]〜（1+）的抗键M-H相互作用相关的虚拟轨道的低能量暗示了与苯胺相互作用的高活性。

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