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Abstract <p>To extend a rarely-studied family of multinuclear [FeFe]-hydrogenase mimics for catalytic proton reduction into hydrogen (H<sub>2</sub>), we carried out the esterification reactions of bridgehead-carboxyl-having diiron azadithiolato precursor [Fe<sub>2</sub>(CO)<sub>6</sub>{(μ-SCH<sub>2</sub>)<sub>2</sub>N(C<sub>6</sub>H<sub>4</sub>CH<sub>2</sub>CO<sub>2</sub>H)}] (<b>1</b>) and three primary alcohols (CH<sub>3</sub>CH<sub>2</sub>OH, (CH<sub>3</sub>)<sub>2</sub>C(CH<sub>2</sub>OH)<sub>2</sub> and CH<sub>3</sub>C(CH<sub>2</sub>OH)<sub>3</sub> to afford three new fully-esterified products [Fe<sub>2</sub>(CO)<sub>6</sub>{(μ-SCH<sub>2</sub>)<sub>2</sub>N(C<sub>6</sub>H<sub>4</sub>CH<sub>2</sub>C[O])}]<sub><i>n</i></sub>R (<i>n</i> = 1, R = OCH<sub>2</sub>CH<sub>3</sub> for diiron <b>2</b>; <i>n</i> = 2, R = (OCH<sub>2</sub>)<sub>2</sub>C(CH<sub>3</sub>)<sub>2</sub> for tetrairon <b>3</b>; and <i>n</i> = 3, R = (OCH<sub>2</sub>)<sub>3</sub>C(CH<sub>3</sub>) for hexairon <b>5</b>) and two new partly-esterified products [Fe<sub>2</sub>(CO)<sub>6</sub>{(μ-SCH<sub>2</sub>)<sub>2</sub>N(C<sub>6</sub>H<sub>4</sub>CH<sub>2</sub>C[O])}]<sub><i>n</i></sub>R (<i>n</i> = 1, R = (OCH<sub>2</sub>)C(CH<sub>3</sub>)<sub>2</sub>(CH<sub>2</sub>OH) for diiron <b>4</b> and <i>n</i> = 2, R = (OCH<sub>2</sub>)<sub>2</sub>C(CH<sub>3</sub>)(CH<sub>2</sub>OH) for tetrairon <b>6</b>). Meanwhile, the fully-esterified iron-sulfur complexes <b>3</b> and <b>5</b> can be obtained in good yield from the complete esterification of their hydoxyl-bearing counterparts <b>4</b> and <b>6</b>, respectively. All the as-obtained new complexes <b>2</b>–<b>6</b> are characterized by means of elemental analysis as well as various spectroscopies, and for <b>2</b> by X-ray crystallography. Further electrochemical investigation of homolog complexes <b>2</b>, <b>3</b> and <b>5</b> is performed without and with acetic acid (HOAc) through cyclic voltammetry (CV), exhibiting that hexairon complex <b>5</b> has a greatest turnover frequency and a lower overpotential for electrocatalytic H<sub>2</sub> evolution among them.</p>

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Synthesis, Structures, and Electrochemical Properties of Multinuclear Iron-Sulfur Complexes Related to [FeFe]-Hydrogenases

  • 期刊论文

  • 发表日期：

    2025年12月1日

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  • Xu-Feng Liu,
  • Ting-Rui Xue,
  • Pei-Hua Zhao

摘要

Abstract

To extend a rarely-studied family of multinuclear [FeFe]-hydrogenase mimics for catalytic proton reduction into hydrogen (H2), we carried out the esterification reactions of bridgehead-carboxyl-having diiron azadithiolato precursor [Fe2(CO)6{(μ-SCH2)2N(C6H4CH2CO2H)}] (1) and three primary alcohols (CH3CH2OH, (CH3)2C(CH2OH)2 and CH3C(CH2OH)3 to afford three new fully-esterified products [Fe2(CO)6{(μ-SCH2)2N(C6H4CH2C[O])}]nR (n = 1, R = OCH2CH3 for diiron 2; n = 2, R = (OCH2)2C(CH3)2 for tetrairon 3; and n = 3, R = (OCH2)3C(CH3) for hexairon 5) and two new partly-esterified products [Fe2(CO)6{(μ-SCH2)2N(C6H4CH2C[O])}]nR (n = 1, R = (OCH2)C(CH3)2(CH2OH) for diiron 4 and n = 2, R = (OCH2)2C(CH3)(CH2OH) for tetrairon 6). Meanwhile, the fully-esterified iron-sulfur complexes 3 and 5 can be obtained in good yield from the complete esterification of their hydoxyl-bearing counterparts 4 and 6, respectively. All the as-obtained new complexes 2–6 are characterized by means of elemental analysis as well as various spectroscopies, and for 2 by X-ray crystallography. Further electrochemical investigation of homolog complexes 2, 3 and 5 is performed without and with acetic acid (HOAc) through cyclic voltammetry (CV), exhibiting that hexairon complex 5 has a greatest turnover frequency and a lower overpotential for electrocatalytic H2 evolution among them.