title: Secondary bonding interactions in biomimetic [2Fe-2S] clusters.
abstract: A series of synthetic [2Fe-2S] complexes with terminal thiophenolate ligands and tethered ether or thioether moieties has been prepared and investigated in order to provide models for the potential interaction of additional donor atoms with the Fe atoms in biological [2Fe-2S] clusters. X-ray crystal structures have been determined for six new complexes that feature appended Et (1(C)), OMe (1(O)), or SMe (1(S)) groups, or with a methylene group (2(C) ), an ether-O (2(O)), or an thioether-S (2(S)) linking two aryl groups. The latter two systems provide a constrained chelate arrangement that induces secondary bonding interactions with the ether-O and thioether-S, which is confirmed by density functional theory (DFT) calculations that also reveal significant spin density on those fifth donor atoms. Structural consequences of the secondary bonding interactions are analyzed in detail, and effects on the spectroscopic and electronic properties are probed by UV-vis, Mössbauer, and (1)H NMR spectroscopy, as well by SQUID measurements and cyclic voltammetry. The potential relevance of the findings for biological [2Fe-2S] sites is considered.
authors.affiliation: Institut für Anorganische Chemie, Georg-August-Universität, Tammannstrasse 4, D-37077 Göttingen, Germany.
authors.forename: Joachim
authors.initials: J
authors.lastname: Ballmann
authors.forename: Sebastian
authors.initials: S
authors.lastname: Dechert
authors.forename: Eckhard
authors.initials: E
authors.lastname: Bill
authors.forename: Ulf
authors.initials: U
authors.lastname: Ryde
authors.forename: Franc
authors.initials: F
authors.lastname: Meyer
mesh_terms: D018360:Crystallography, X-Ray; D007501:Iron / Q000737:chemistry*; D008958:Models, Molecular; D018716:Molecular Mimicry; D013455:Sulfur / Q000737:chemistry*
chemical_list: D013455:Sulfur; D007501:Iron