Cyclic tetranuclear iron-carbonyl complex containing thiobisbenzenethiolate ligands: Synthesis and structural characterization
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.
iron clusters, hydrogenase model, iron carbonyls, metallacycle, macromolecule
Johnson, Shakeena L., Nikolay N. Gerasimchuk, and Charles A. Mebi. "Cyclic tetranuclear iron-carbonyl complex containing thiobisbenzenethiolate ligands: Synthesis and structural characterization." Inorganica Chimica Acta 477 (2018): 306-311.
Inorganica Chimica Acta