Dimeric FeFe-hydrogenase mimics bearing carboxylic acids: Synthesis and electrochemical investigation

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• 作者：Benjamin R. Garrett ; Amneh Awad ; Mingfu He ; Kevin A. Click ; Christopher B. Durr ; Judith C. Gallucci ; Christopher M. Hadad ; Yiying Wu ; ^{wu@chemistry.ohio-state.edu" class="auth_mail" title="E-mail the corresponding author}
• 关键词：FeFe hydrogenase mimic ; Electrochemical degradation mechanism ; Surface immobilization ; Catalysis ; Water splitting
• 刊名：Polyhedron
• 出版年：2016
• 出版时间：8 January 2016
• 年：2016
• 卷：103
• 期：part_PA
• 页码：21-27
• 全文大小：1587 K

文摘

Hydrogen is expected to be important for future sustainable energy applications. Recent interest in adsorbing water splitting catalysts on a semiconductor surface for electrocatalytic hydrogen production warrants careful study of electrocatalysts with functional groups capable of binding to a surface. The monomeric complex Fe₂(μ-S₂(CH₂)₃)(CO)₅PPh₂C₆H₄CO₂H (S₂(CH₂)₃ = 1,3-propanedithiolate, pdt) and the dimeric complexes [{Fe₂(μ-pdt)(CO)₅}₂(μ,κ¹,κ¹-Ph₂PCH₂N(Ar)CH₂PPh₂)] (Ar = p-CO₂H-Ph, 3,5-CO₂HPh, p-CH₂CO₂HPh, m-CO₂H-Ph) bearing carboxylic acid functional groups have been prepared. The first electrochemical study of these dimeric FeFe complexes indicate that the complexes degrade upon reduction to form the species [Fe₂(μ-pdt)(CO)₄(κ²-Ph₂PCH₂N(Ar)CH₂PPh₂)]. A route is proposed for the formation of [Fe₂(μ-pdt)(CO)₄(κ²-Ph₂PCH₂N(Ar)CH₂PPh₂)] from [{Fe₂(μ-pdt)(CO)₅}₂(μ,κ¹,κ¹-Ph₂PCH₂N(Ar)CH₂PPh₂)] and a crystal structure of an intermediate in the proposed electrochemical degradation pathway is presented. The electrochemical study presented herein provides valuable insight into degradation pathways of FeFe hydrogenase mimics bearing carboxylic acids amenable to surface immobilization.