{"title":"Azadithiolate-bridged [FeFe]-hydrogenase mimics with bridgehead N-derivation: structural and electrochemical investigations","authors":"Ming-Sheng Gui, Yu Guan, Yu-Long Li, Pei-Hua Zhao","doi":"10.1007/s11243-022-00508-5","DOIUrl":null,"url":null,"abstract":"<div><p>To further develop the active site mimics of azadithiolate-bridged [FeFe]-hydrogenases, a series of new diiron azadithiolate complexes [{(<i>μ</i>-SCH<sub>2</sub>)<sub>2</sub>N(C<sub>6</sub>H<sub>4</sub>CH<sub>2</sub>CH<sub>2</sub>OC(O)R)}Fe<sub>2</sub>(CO)<sub>6</sub>] (R = CH<sub>2</sub>C<sub>6</sub>H<sub>4</sub>Me-<i>p</i>, <b>2</b>; C<sub>6</sub>H<sub>5</sub>, <b>3</b>; CH<sub>3</sub>, <b>4</b>) bearing bridgehead N-derivation were successfully prepared by facile esterification reaction of parent complex [{(<i>μ</i>-SCH<sub>2</sub>)<sub>2</sub>N(C<sub>6</sub>H<sub>4</sub>CH<sub>2</sub>CH<sub>2</sub>OH)}Fe<sub>2</sub>(CO)<sub>6</sub>] (<b>1</b>) and different carboxyl compounds RCO<sub>2</sub>H in the presence of 4-dimethylaminopyridine (DMAP) as catalyst and dicyclohexylcarbodiimide (DCC) as dehydrating reagent. Complexes <b>2–4</b> have been fully characterized by means of elemental analysis, FT-IR and NMR (<sup>1</sup>H, <sup>13</sup>C) spectroscopies, and especially for <b>2</b> by X-ray crystallography. Further electrochemical and electrocatalytic properties of target complexes <b>2</b>–<b>4</b> and reference analogue <b>1</b> were studied and compared in the absence and presence of acetic acid (HOAc) as a proton source by cyclic voltammetry (CV), indicating that they may be considered as the active biomimetic electrocatalysts for proton reduction to hydrogen (H<sub>2</sub>).\n</p></div>","PeriodicalId":803,"journal":{"name":"Transition Metal Chemistry","volume":null,"pages":null},"PeriodicalIF":1.6000,"publicationDate":"2022-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Transition Metal Chemistry","FirstCategoryId":"92","ListUrlMain":"https://link.springer.com/article/10.1007/s11243-022-00508-5","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
Abstract
To further develop the active site mimics of azadithiolate-bridged [FeFe]-hydrogenases, a series of new diiron azadithiolate complexes [{(μ-SCH2)2N(C6H4CH2CH2OC(O)R)}Fe2(CO)6] (R = CH2C6H4Me-p, 2; C6H5, 3; CH3, 4) bearing bridgehead N-derivation were successfully prepared by facile esterification reaction of parent complex [{(μ-SCH2)2N(C6H4CH2CH2OH)}Fe2(CO)6] (1) and different carboxyl compounds RCO2H in the presence of 4-dimethylaminopyridine (DMAP) as catalyst and dicyclohexylcarbodiimide (DCC) as dehydrating reagent. Complexes 2–4 have been fully characterized by means of elemental analysis, FT-IR and NMR (1H, 13C) spectroscopies, and especially for 2 by X-ray crystallography. Further electrochemical and electrocatalytic properties of target complexes 2–4 and reference analogue 1 were studied and compared in the absence and presence of acetic acid (HOAc) as a proton source by cyclic voltammetry (CV), indicating that they may be considered as the active biomimetic electrocatalysts for proton reduction to hydrogen (H2).
期刊介绍:
Transition Metal Chemistry is an international journal designed to deal with all aspects of the subject embodied in the title: the preparation of transition metal-based molecular compounds of all kinds (including complexes of the Group 12 elements), their structural, physical, kinetic, catalytic and biological properties, their use in chemical synthesis as well as their application in the widest context, their role in naturally occurring systems etc.
Manuscripts submitted to the journal should be of broad appeal to the readership and for this reason, papers which are confined to more specialised studies such as the measurement of solution phase equilibria or thermal decomposition studies, or papers which include extensive material on f-block elements, or papers dealing with non-molecular materials, will not normally be considered for publication. Work describing new ligands or coordination geometries must provide sufficient evidence for the confident assignment of structural formulae; this will usually take the form of one or more X-ray crystal structures.