Trinuclear [NiFe] Clusters as Structural Models for [NiFe] Hydrogenase Active Sites

Heinemann FW (2005)


Publication Type: Journal article

Publication year: 2005

Journal

Pages Range: 371-377

DOI: 10.1002/ejic.200400587

Abstract

[Fe(CH3COCH=CHPh)(CO)3] reacts with [Ni(′S 4′)]x (x = 1, 2) or [Ni(′S4C 3Me2′)] [′S4′2- = 1,2-bis(2-mercaptophenylthio)-ethane(2-), ′S4C 3Me2′2- = 1,3-bis(2-mercaptophenylthio)- 2,2-dimethylpropane(2-)] to afford trinuclear [NiFe] clusters [Ni(′S 4′){Fe(CO)3}2] (1) and [Ni(′S 4C3Me2′){Fe(CO)3} 2] (2) and the dinuclear FeIIFe0 complex [Fe(CO)(′S4C3Me2′)Fe(CO) 3] (3). Clusters 1 and 2 have Ni-Fe bond lengths similar to those of active or reduced states of [NiFe] hydrogenases, a sulfur-dominated coordination sphere of Ni and iron-bound CO. Therefore, 1 and 2 may serve as structural model complexes for the [NiFe] hydrogenase active site. Combination of the prime;S4C3Me2′ ligand with FeCl 2·4H2O yielded [Fe(′S4C 3Me2′)]2 (4), the dinuclearity of which suggests that the ′S4C3Me2′ ligand is less flexible than its ethylene-bridged derivative, which affords a tetrameric [Fe(′S4′)]4 complex reported earlier. Compound 4 reacts with 2 equiv. of CO to give [Fe(CO)(′S 4C3Me2′)]2 (5), which like 4 is only sparingly soluble in all common organic solvents. Complex 5 easily loses CO even if stored in the solid state. [Fe(CH3COCH= CHPh)(CO) 3] reacts with 5 to afford 3 as the only product. © Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005.

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How to cite

APA:

Heinemann, F.W. (2005). Trinuclear [NiFe] Clusters as Structural Models for [NiFe] Hydrogenase Active Sites. European Journal of Inorganic Chemistry, 371-377. https://doi.org/10.1002/ejic.200400587

MLA:

Heinemann, Frank Wilhelm. "Trinuclear [NiFe] Clusters as Structural Models for [NiFe] Hydrogenase Active Sites." European Journal of Inorganic Chemistry (2005): 371-377.

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