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Tetranuclear Iron C...
Tetranuclear Iron Complexes Bearing Benzenetetrathiolate Bridges as Four-Electron Transformation Templates and Their Electrocatalytic Properties for Proton Reduction
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Chen, Lin (författare)
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Wang, Mei (författare)
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Gloaguen, Frederic (författare)
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Zheng, Dehua (författare)
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Zhang, Peili (författare)
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- Sun, Licheng (författare)
- KTH,Organisk kemi
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(creator_code:org_t)
- 2013-01-31
- 2013
- Engelska.
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Ingår i: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 52:4, s. 1798-1806
- Relaterad länk:
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https://urn.kb.se/re...
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https://doi.org/10.1...
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Abstract
Ämnesord
Stäng
- Two tetranuclear iron-sulfur complexes, (mu,mu-pbtt)[Fe-2(CO)(6)](2) (pbtt = benzene-1,2,4,5-tetrathiolato, 3) and (mu,mu-obtt)[Fe-2(CO)(6)](2) (obtt = benzene-1,2,3,4-tetrathiolato, 4), were prepared from reaction of Fe-3(CO)(12) and the corresponding tetramercaptobenzene in THF, respectively. Complexes 5 and 6, (mu,mu-pbtt)[Fe-2(CO)(5)L-1][Fe-2(CO)(5)L-2] (L-1 = CO, L-2 = PPyr(3) (Pyr = N-pyrrolyl), 5; L-1 = L-2 = PPyr(3), 6) were obtained by controlling CO displacement of 3 with PPyr(3). Molecular structures of 3-6 were determined by spectroscopic and single-crystal X-ray analyses. All-CO Fe4S4 complexes 3 and 4 each display four-electron reduction processes in consecutive chemically reversible two-electron reduction events with relatively narrow potential spans in the cyclic voltammograms. Phosphine-substituted Fe4S4 complexes 5 and 6 exhibit two consecutive two-electron reduction events, which are not fully reversible. The electrocatalytic properties of 3 and 4 for proton reduction were studied using a series of carboxylic acids of increasing strength (CH3COOH, CH2ClCOOH, CHCl2COOH, CCl3COOH, and CF3COOH). The mechanisms for electrochemical proton reduction to hydrogen catalyzed by complex 3 as a function of acid strength are discussed.
Ämnesord
- NATURVETENSKAP -- Kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences (hsv//eng)
Nyckelord
- Fe-Only Hydrogenases
- Active-Site Models
- X-Ray Structures
- Electrochemical Properties
- Organometallic Complex
- Hexacarbonyl Complexes
- H-2 Evolution
- Diiron
- Ligands
- Catalysis
Publikations- och innehållstyp
- ref (ämneskategori)
- art (ämneskategori)
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