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Synthesis, Characterization, and Reactivity of Functionalized Trinuclear Iron-Sulfur Clusters - A New Class of Bioinspired Hydrogenase Models.

Kaiser M, Knör G - Eur J Inorg Chem (2015)

Bottom Line: Two alternative synthetic routes based on different thionation reactions of triiron dodecacarbonyl were tested.The catalytic reactivity of the trinuclear iron-sulfur cluster core for proton reduction in solution at low overpotential was demonstrated.These deeply colored bisphosphine-bridged sulfur-capped iron carbonyl systems are discussed as promising candidates for the development of new bioinspired model compounds of iron-based hydrogenases.

View Article: PubMed Central - PubMed

Affiliation: Institute of Inorganic Chemistry, Johannes Kepler University Linz (JKU) , Altenbergerstr. 69, 4040 Linz, Austria , http://www.anorganik.jku.at.

ABSTRACT

The air- and moisture-stable iron-sulfur carbonyl clusters Fe3S2(CO)7(dppm) (1) and Fe3S2(CO)7(dppf) (2) carrying the bisphosphine ligands bis(diphenylphosphanyl)methane (dppm) and 1,1'-bis(diphenylphosphanyl)ferrocene (dppf) were prepared and fully characterized. Two alternative synthetic routes based on different thionation reactions of triiron dodecacarbonyl were tested. The molecular structures of the methylene-bridged compound 1 and the ferrocene-functionalized derivative 2 were determined by single-crystal X-ray diffraction. The catalytic reactivity of the trinuclear iron-sulfur cluster core for proton reduction in solution at low overpotential was demonstrated. These deeply colored bisphosphine-bridged sulfur-capped iron carbonyl systems are discussed as promising candidates for the development of new bioinspired model compounds of iron-based hydrogenases.

No MeSH data available.


Solution FTIR spectra of the iron–sulfur clusters (a) 1 and (b) 2 in the carbonyl stretching vibration region (298 K, CH2Cl2).
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fig01: Solution FTIR spectra of the iron–sulfur clusters (a) 1 and (b) 2 in the carbonyl stretching vibration region (298 K, CH2Cl2).

Mentions: The FTIR spectra of the triiron clusters were measured both in solution and in the solid phase. Notably, the KBr pellet data of 2 were characterized by a broadened and almost featureless peak pattern (see the Supporting Information), which sometimes occurs for this class of compounds in the solid state.20 Well-resolved spectra could be obtained for both clusters only in the liquid phase. The infrared spectrum of the iron–sulfur complex 1 in CH2Cl2 solution displays a set of three main carbonyl band maxima and two additional shoulders in the = 1900–2100 cm–1 region for ν(CO) stretching vibration (Figure1). A quite similar FTIR pattern is observed for 2; however, the two additional ν(CO) shoulders at = 1987 and 1962 cm–1 are better resolved and more intense.


Synthesis, Characterization, and Reactivity of Functionalized Trinuclear Iron-Sulfur Clusters - A New Class of Bioinspired Hydrogenase Models.

Kaiser M, Knör G - Eur J Inorg Chem (2015)

Solution FTIR spectra of the iron–sulfur clusters (a) 1 and (b) 2 in the carbonyl stretching vibration region (298 K, CH2Cl2).
© Copyright Policy
Related In: Results  -  Collection

Show All Figures
getmorefigures.php?uid=PMC4612652&req=5

fig01: Solution FTIR spectra of the iron–sulfur clusters (a) 1 and (b) 2 in the carbonyl stretching vibration region (298 K, CH2Cl2).
Mentions: The FTIR spectra of the triiron clusters were measured both in solution and in the solid phase. Notably, the KBr pellet data of 2 were characterized by a broadened and almost featureless peak pattern (see the Supporting Information), which sometimes occurs for this class of compounds in the solid state.20 Well-resolved spectra could be obtained for both clusters only in the liquid phase. The infrared spectrum of the iron–sulfur complex 1 in CH2Cl2 solution displays a set of three main carbonyl band maxima and two additional shoulders in the = 1900–2100 cm–1 region for ν(CO) stretching vibration (Figure1). A quite similar FTIR pattern is observed for 2; however, the two additional ν(CO) shoulders at = 1987 and 1962 cm–1 are better resolved and more intense.

Bottom Line: Two alternative synthetic routes based on different thionation reactions of triiron dodecacarbonyl were tested.The catalytic reactivity of the trinuclear iron-sulfur cluster core for proton reduction in solution at low overpotential was demonstrated.These deeply colored bisphosphine-bridged sulfur-capped iron carbonyl systems are discussed as promising candidates for the development of new bioinspired model compounds of iron-based hydrogenases.

View Article: PubMed Central - PubMed

Affiliation: Institute of Inorganic Chemistry, Johannes Kepler University Linz (JKU) , Altenbergerstr. 69, 4040 Linz, Austria , http://www.anorganik.jku.at.

ABSTRACT

The air- and moisture-stable iron-sulfur carbonyl clusters Fe3S2(CO)7(dppm) (1) and Fe3S2(CO)7(dppf) (2) carrying the bisphosphine ligands bis(diphenylphosphanyl)methane (dppm) and 1,1'-bis(diphenylphosphanyl)ferrocene (dppf) were prepared and fully characterized. Two alternative synthetic routes based on different thionation reactions of triiron dodecacarbonyl were tested. The molecular structures of the methylene-bridged compound 1 and the ferrocene-functionalized derivative 2 were determined by single-crystal X-ray diffraction. The catalytic reactivity of the trinuclear iron-sulfur cluster core for proton reduction in solution at low overpotential was demonstrated. These deeply colored bisphosphine-bridged sulfur-capped iron carbonyl systems are discussed as promising candidates for the development of new bioinspired model compounds of iron-based hydrogenases.

No MeSH data available.