Article ; Online: Bulky oxadithiolate-bridged [FeFe]‑hydrogenase mimics [Fe<sub>2</sub>(μ-R<sub>2</sub>odt)(CO)<sub>4</sub>(κ<sup>2</sup>-diphosphine)] (R = Ph and H) with chelating diphosphines.
Journal of inorganic biochemistry
2022 Volume 235, Page(s) 111933
Abstract: ... complexes [Fe2(μ-R2odt)(CO)4(κ2-diphosphine)] (3-5) with bulky ... from the Me3NO-assisted substitutions of diiron hexacarbonyl precursors [Fe2(μ-R26] (R2odt = (SCHR)2O, R = Ph (1) and H (2)) with different ...
| Abstract | In order to develop an attractive generation of bulky oxadithiolate-bridged [FeFe]‑hydrogenase mimics with chelating diphosphines, two new series of asymmetrically diphosphine-substituted diiron model complexes [Fe<sub>2</sub>(μ-R<sub>2</sub>odt)(CO)<sub>4</sub>(κ<sup>2</sup>-diphosphine)] (3-5) with bulky Ph<sub>2</sub>odt bridge and their reference counterparts (6-8) with common odt bridge were obtained from the Me<sub>3</sub>NO-assisted substitutions of diiron hexacarbonyl precursors [Fe<sub>2</sub>(μ-R<sub>2</sub>odt)(CO)<sub>6</sub>] (R<sub>2</sub>odt = (SCHR)<sub>2</sub>O, R = Ph (1) and H (2)) with different diphosphines such as (Ph<sub>2</sub>P)<sub>2</sub>NBn (labelled PN<sup>Bn</sup>P, Bn = benzyl), (Ph<sub>2</sub>PCH<sub>2</sub>)<sub>2</sub>NBn (PCN<sup>Bn</sup>CP), and (Ph<sub>2</sub>PCH<sub>2</sub>)<sub>2</sub>CH<sub>2</sub> (DPPP)), respectively. All the as-prepared complexes have been characterized by elemental analysis, IR plus NMR spectroscopies, and particularly by X-ray crystallography for 3-8. It is interesting to note that complexes 3 and 6 chelating by small bite-angle PN<sup>Bn</sup>P diphosphine have the favorable dibasal isomer whereas analogues 4, 5 and 7, 8 chelating by flexible backbone PCN<sup>Bn</sup>CP or DPPP ligands possess the main apical-basal isomer in solution or in the solid state. Further, the electrochemical properties of two pairs of representative complexes 3, 6 and 5, 8 are explored and compared by cyclic voltammetry (CV) in the absence and presence of trifluoroacetic acid (CF<sub>3</sub>CO<sub>2</sub>H) as proton source, indicating that the complete protonations of 3, 6 and 5, 8 with higher concentration of CF<sub>3</sub>CO<sub>2</sub>H lead to two new catalytic waves for the electrocatalytic proton reduction to hydrogen (H<sub>2</sub>). |
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| MeSH term(s) | Chelating Agents ; Crystallography, X-Ray ; Hydrogenase/chemistry ; Iron-Sulfur Proteins/chemistry ; Phosphines/chemistry ; Pregnenolone Carbonitrile ; Protons |
| Chemical Substances | Chelating Agents ; Iron-Sulfur Proteins ; Phosphines ; Protons ; Pregnenolone Carbonitrile (1434-54-4) ; Hydrogenase (EC 1.12.7.2) |
| Language | English |
| Publishing date | 2022-07-14 |
| Publishing country | United States |
| Document type | Journal Article ; Research Support, Non-U.S. Gov't |
| ZDB-ID | 162843-4 |
| ISSN | 1873-3344 ; 0162-0134 |
| ISSN (online) | 1873-3344 |
| ISSN | 0162-0134 |
| DOI | 10.1016/j.jinorgbio.2022.111933 |
| Database | MEDical Literature Analysis and Retrieval System OnLINE |
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