Tertiary phosphine‐supported diiron model complexes relevant to [FeFe]‐hydrogenases
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| Natura: | Artículo Open Access |
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Wiley
2024
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| _version_ | 1867021383851048960 |
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| author | Yan Gao Bo Jin Jin‐Liang Zhang Xing‐Bin Jing Pei‐Hua Zhao |
| author_facet | Yan Gao Bo Jin Jin‐Liang Zhang Xing‐Bin Jing Pei‐Hua Zhao Yan Gao Bo Jin Jin‐Liang Zhang Xing‐Bin Jing Pei‐Hua Zhao |
| collection | Wiley Open Access |
| contents | Tertiary phosphine‐supported diiron model complexes relevant to [FeFe]‐hydrogenases Yan Gao Bo Jin Jin‐Liang Zhang Xing‐Bin Jing Pei‐Hua Zhao Applied Organometallic Chemistry In an effort to better probe the structure–function relationship on the biological [Fe4S4] cluster of [FeFe]‐hydrogenases, a new library of tertiary phosphine‐supported diiron dithiolate complexes [Fe2(μ‐adtNR)(CO)5{P(C6H4X)3}] (1–3) with various substituents (X = F vs. H vs. Me), wherein adtNR is denoted as abbreviation for the (SCH2)2N(C6H4C2H4OC(O)CH2C6H4Me) unit, is prepared as the active site mimics of [FeFe]‐hydrogenases. Notably, the substituent influences of tertiary phosphines on the structures and electrochemical behaviors of 1–3 are studied by spectroscopic and crystallographic techniques as well as cyclic voltammetry. For example, the electronic effect of tertiary phosphines [P(C6H4X)3] is responsible for the electron density around diiron center and the key Fe–Fe as well as Fe–P lengths in 1–3 as revealed by IR spectroscopy and crystallographic analysis. Further, complexes 1–3 show the electrochemical activity for proton reduction into molecular hydrogen (H2) using acetic acid (AcOH) as a proton source. Noticeably, F‐substituent‐containing diiron model complex 1 exhibits greater turnover frequency (i.e., turnover frequency value) and similar overpotential for electrocatalytic H2 evolution relative to H‐ or Me‐substituent‐bearing diiron homologs 2 or 3. 10.1002/aoc.7608 http://onlinelibrary.wiley.com/termsAndConditions#vor |
| doi_str_mv | 10.1002/aoc.7608 |
| format | Artículo Open Access |
| id | wiley_oa_10_1002_aoc_7608 |
| institution | Wiley Open Access |
| license_str_mv | http://onlinelibrary.wiley.com/termsAndConditions#vor |
| publishDate | 2024 |
| publisher | Wiley |
| record_format | wiley_oa |
| spellingShingle | Tertiary phosphine‐supported diiron model complexes relevant to [FeFe]‐hydrogenases Yan Gao Bo Jin Jin‐Liang Zhang Xing‐Bin Jing Pei‐Hua Zhao Applied Organometallic Chemistry Tertiary phosphine‐supported diiron model complexes relevant to [FeFe]‐hydrogenases Yan Gao Bo Jin Jin‐Liang Zhang Xing‐Bin Jing Pei‐Hua Zhao Applied Organometallic Chemistry In an effort to better probe the structure–function relationship on the biological [Fe4S4] cluster of [FeFe]‐hydrogenases, a new library of tertiary phosphine‐supported diiron dithiolate complexes [Fe2(μ‐adtNR)(CO)5{P(C6H4X)3}] (1–3) with various substituents (X = F vs. H vs. Me), wherein adtNR is denoted as abbreviation for the (SCH2)2N(C6H4C2H4OC(O)CH2C6H4Me) unit, is prepared as the active site mimics of [FeFe]‐hydrogenases. Notably, the substituent influences of tertiary phosphines on the structures and electrochemical behaviors of 1–3 are studied by spectroscopic and crystallographic techniques as well as cyclic voltammetry. For example, the electronic effect of tertiary phosphines [P(C6H4X)3] is responsible for the electron density around diiron center and the key Fe–Fe as well as Fe–P lengths in 1–3 as revealed by IR spectroscopy and crystallographic analysis. Further, complexes 1–3 show the electrochemical activity for proton reduction into molecular hydrogen (H2) using acetic acid (AcOH) as a proton source. Noticeably, F‐substituent‐containing diiron model complex 1 exhibits greater turnover frequency (i.e., turnover frequency value) and similar overpotential for electrocatalytic H2 evolution relative to H‐ or Me‐substituent‐bearing diiron homologs 2 or 3. 10.1002/aoc.7608 http://onlinelibrary.wiley.com/termsAndConditions#vor |
| title | Tertiary phosphine‐supported diiron model complexes relevant to [FeFe]‐hydrogenases |
| topic | Applied Organometallic Chemistry |
| url | https://onlinelibrary.wiley.com/doi/10.1002/aoc.7608 |