Cyclic tetranuclear iron-carbonyl complex containing thiobisbenzenethiolate ligands: Synthesis and structural characterization

Abstract

A new macromolecular double-butterfly Fe/S carbonyl cluster, [Fe2(CO)6]2(μ-4,4'-thiobisbenzenethiolato)2 (1), a model for the active site of [Fe-Fe] hydrogenases, has been prepared and characterized by spectroscopic methods and X-ray crystallography. The molecular structure of 1 contains two units of S2Fe2(CO)6 covalently linked to two thiobisbenzene groups to form a 26-membered metallocycle with the benzene substituents on sulfur adopting an ae stereochemistry. The Fe-Fe bond in 1 is 2.5046(5) Å which is close to that of the enzyme and related complexes. Crystals of 1 obtained from dichlormethane solution of [Fe2(CO)6]2(μ-4,4'-thiobisbenzenethiolato)2 contain two dichloromethane molecules trapped in the cavity of 1. Infrared spectrum of 1 has peaks at 2071, 2030, and 1972 cm-1 charateristic of the presence of the Fe2(CO)6 core. Spectroscopic evidence suggest significant electronic interaction between the thiobisbenzene moieties and the S2Fe2(CO)6 units in 1.

Department(s)

Chemistry and Biochemistry

Document Type

Article

DOI

https://doi.org/10.1016/j.ica.2018.03.043

Keywords

iron clusters, hydrogenase model, iron carbonyls, metallacycle, macromolecule

Publication Date

2018

Journal Title

Inorganica Chimica Acta

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