Pei-Hua Zhao, Yan Gao, Yu-Long Sun, Xing-Bin Jing, Diao-Yu Zhou
{"title":"Biomimics of [FeFe]‑hydrogenases: Diiron aza- versus oxadiphenylpropanedithiolate complexes with mono- versus diphosphines","authors":"Pei-Hua Zhao, Yan Gao, Yu-Long Sun, Xing-Bin Jing, Diao-Yu Zhou","doi":"10.1016/j.jinorgbio.2025.112859","DOIUrl":null,"url":null,"abstract":"<div><div>To extensively devolep the bioinspired chemistry of [FeFe]‑hydrogenases, this study performs an insigt into the selective substitution of all‑carbonyl diiron aza- versus oxadiphenylpropanedithiolate precursors Fe<sub>2</sub>(<em>μ</em>-Ph<sub>2</sub>xdt)(CO)<sub>6</sub> (Ph<sub>2</sub>xdt = Ph<sub>2</sub>odt = (SCHPh)<sub>2</sub>O for <strong>1</strong> and Ph<sub>2</sub>adt<sup>NH</sup> = (SCHPh)<sub>2</sub>NH for <strong>2</strong>) by mono- versus diphosphines P(C<sub>6</sub>H<sub>4</sub>R-<em>p</em>)<sub>3</sub> (R = Me and Cl) and (Ph<sub>2</sub>P)<sub>2</sub>R′ (R′ = <em>cis</em>-CH=CH- for dppv and -CH<sub>2</sub>CH<sub>2</sub>- for dppe). With monophosphines, their monosubstituted diiron Ph<sub>2</sub>odt complexes Fe<sub>2</sub>(<em>μ</em>-Ph<sub>2</sub>odt)(CO)<sub>5</sub>){<em>κ</em><sup>1</sup>-P(C<sub>6</sub>H<sub>4</sub>R-<em>p</em>)<sub>3</sub>} (R = Me for <strong>1a</strong> and Cl for <strong>1b</strong>) were obtained through the oxidative decarbonylating of <strong>1</strong> at room temperature in MeCN with Me<sub>3</sub>NO·2H<sub>2</sub>O; in contrast, analogous diiron Ph<sub>2</sub>adt<sup>NH</sup> complexes Fe<sub>2</sub>(<em>μ</em>-Ph<sub>2</sub>adt<sup>NH</sup>)(CO)<sub>5</sub>){<em>κ</em><sup>1</sup>-P(C<sub>6</sub>H<sub>4</sub>R-<em>p</em>)<sub>3</sub>} (R = Me for <strong>2a</strong> and Cl for <strong>2b</strong>) were afforded via the photolytic decarbonlating of <strong>2</strong> under UV irradiation (365 nm) in toluene. With diphosphines, the dppv-chelated diiron Ph<sub>2</sub>xdt complexes Fe<sub>2</sub>(<em>μ</em>-Ph<sub>2</sub>xdt)(CO)<sub>4</sub>(<em>κ</em><sup>2</sup>-dppv) (Ph<sub>2</sub>xdt = Ph<sub>2</sub>odt for <strong>1c</strong> and Ph<sub>2</sub>adt<sup>NH</sup> for <strong>2c</strong>) were prepared from the UV-irradiated decarbonylation of <strong>1</strong> or <strong>2</strong> in toluene; by contrast, the dppe-chelated diiron similar complexes Fe<sub>2</sub>(<em>μ</em>-Ph<sub>2</sub>xdt)(CO)<sub>4</sub>(<em>κ</em><sup>2</sup>-dppe) (Ph<sub>2</sub>xdt = Ph<sub>2</sub>odt for <strong>1d</strong> and Ph<sub>2</sub>adt<sup>NH</sup> for <strong>2d</strong>) were synthesized from the Me<sub>3</sub>NO-assisted decarbonylation of <strong>1</strong> in room-temperature MeCN and that of <strong>2</strong> at refluxing toluene, respectively. The elemental analysis, FT-IR and NMR (<sup>1</sup>H, <sup>31</sup>P) spectroscopy are used for the full elucidation of the molecular structures of these new diiron complexes and X-ray crystallography is applied for further confirmation of <strong>1</strong>, <strong>2</strong> and <strong>1a</strong>, <strong>2b</strong>. The electrochemical properties of representative complexes <strong>1</strong>, <strong>1a</strong>, <strong>1c</strong> and <strong>2</strong>, <strong>2a</strong>, <strong>2c</strong> have been explored and compared with and without acetic acid (AcOH).</div></div>","PeriodicalId":364,"journal":{"name":"Journal of Inorganic Biochemistry","volume":"267 ","pages":"Article 112859"},"PeriodicalIF":3.8000,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Inorganic Biochemistry","FirstCategoryId":"99","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S016201342500039X","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"BIOCHEMISTRY & MOLECULAR BIOLOGY","Score":null,"Total":0}
引用次数: 0
Abstract
To extensively devolep the bioinspired chemistry of [FeFe]‑hydrogenases, this study performs an insigt into the selective substitution of all‑carbonyl diiron aza- versus oxadiphenylpropanedithiolate precursors Fe2(μ-Ph2xdt)(CO)6 (Ph2xdt = Ph2odt = (SCHPh)2O for 1 and Ph2adtNH = (SCHPh)2NH for 2) by mono- versus diphosphines P(C6H4R-p)3 (R = Me and Cl) and (Ph2P)2R′ (R′ = cis-CH=CH- for dppv and -CH2CH2- for dppe). With monophosphines, their monosubstituted diiron Ph2odt complexes Fe2(μ-Ph2odt)(CO)5){κ1-P(C6H4R-p)3} (R = Me for 1a and Cl for 1b) were obtained through the oxidative decarbonylating of 1 at room temperature in MeCN with Me3NO·2H2O; in contrast, analogous diiron Ph2adtNH complexes Fe2(μ-Ph2adtNH)(CO)5){κ1-P(C6H4R-p)3} (R = Me for 2a and Cl for 2b) were afforded via the photolytic decarbonlating of 2 under UV irradiation (365 nm) in toluene. With diphosphines, the dppv-chelated diiron Ph2xdt complexes Fe2(μ-Ph2xdt)(CO)4(κ2-dppv) (Ph2xdt = Ph2odt for 1c and Ph2adtNH for 2c) were prepared from the UV-irradiated decarbonylation of 1 or 2 in toluene; by contrast, the dppe-chelated diiron similar complexes Fe2(μ-Ph2xdt)(CO)4(κ2-dppe) (Ph2xdt = Ph2odt for 1d and Ph2adtNH for 2d) were synthesized from the Me3NO-assisted decarbonylation of 1 in room-temperature MeCN and that of 2 at refluxing toluene, respectively. The elemental analysis, FT-IR and NMR (1H, 31P) spectroscopy are used for the full elucidation of the molecular structures of these new diiron complexes and X-ray crystallography is applied for further confirmation of 1, 2 and 1a, 2b. The electrochemical properties of representative complexes 1, 1a, 1c and 2, 2a, 2c have been explored and compared with and without acetic acid (AcOH).
期刊介绍:
The Journal of Inorganic Biochemistry is an established international forum for research in all aspects of Biological Inorganic Chemistry. Original papers of a high scientific level are published in the form of Articles (full length papers), Short Communications, Focused Reviews and Bioinorganic Methods. Topics include: the chemistry, structure and function of metalloenzymes; the interaction of inorganic ions and molecules with proteins and nucleic acids; the synthesis and properties of coordination complexes of biological interest including both structural and functional model systems; the function of metal- containing systems in the regulation of gene expression; the role of metals in medicine; the application of spectroscopic methods to determine the structure of metallobiomolecules; the preparation and characterization of metal-based biomaterials; and related systems. The emphasis of the Journal is on the structure and mechanism of action of metallobiomolecules.