Search: onr:"swepub:oai:DiVA.org:kth-16892" >
Protonation, electr...
Protonation, electrochemical properties and molecular structures of halogen-functionalized diiron azadithiolate complexes related to the active site of iron-only hydrogenases
-
Wang, Fujun (author)
-
Wang, Mei (author)
-
Liu, Xiaoyang (author)
-
show more...
-
Jin, Kun (author)
-
Donga, Weibing (author)
-
- Sun, Licheng (author)
- KTH,Organisk kemi
-
show less...
-
(creator_code:org_t)
- Royal Society of Chemistry (RSC), 2007
- 2007
- English.
-
In: Dalton Transactions. - : Royal Society of Chemistry (RSC). - 1477-9226 .- 1477-9234. ; :34, s. 3812-3819
- Related links:
-
https://urn.kb.se/re...
-
show more...
-
https://doi.org/10.1...
-
show less...
Abstract
Subject headings
Close
- Diiron complexes [{( mu-SCH2) 2NCH(2)C(6)H(4)X}{Fe( CO)(2)L}(2)] ( L = CO, X = 2-Br, 1; 2-F, 2; 3-Br, 3; L = PMe3, X = 2-Br, 4) were prepared as biomimetic models of the iron-only hydrogenase active site. The N-protonated species [ 1( NH)]+ClO4-, [ 2( NH)]+ClO4- and the mu-hydride diiron complex [ 4( FeHFe)]+PF6- were obtained in the presence of proton acids and well characterized. The protonation process of 4 was studied by in-situ IR and NMR spectroscopy, which suggests the formation of the diprotonated species [ 4( NH)( FeHFe)](2+) in the presence of an excess of proton acid. The molecular structures of 1, [ 1( NH)]+ClO4-, 4 and [ 4( FeHFe)]+PF6- were determined by X-ray crystallography. The single-crystal X-ray analysis reveals that an intramolecular H center dot center dot center dot Br contact ( 2.82 angstrom) in the crystalline state of [ 1( NH)]+ClO4-. In the presence of 1-6 equiv of the stronger acid HOTf, complex 1 is readily protonated on the bridged-N atom and can electrochemically catalyze the proton reduction at a relatively mild potential ( ca. -1.0 V). Complex 4 is also electrocatalytic active at -1.4 V in the presence of HOTf with formation of the mu-hydride diiron species.
Keyword
- desulfovibrio-desulfuricans
- bridging ligand
- model complexes
- h-2 evolution
- coordination
- reduction
- catalysis
- relevant
- hydride
- cluster
Publication and Content Type
- ref (subject category)
- art (subject category)
Find in a library
To the university's database