A Dinuclear Iron Complex with Two Cofacial [FeS₄] Cores Linked by Covalent Ligand Periphery Clamps and Dissociable Thiolate Bridges

Abstract

As part of a long‐term study of dinuclear iron complexes with sulfur‐rich coordination spheres and cofacial, sterically variable binding sites for molecules relevant to nitrogenase, the complex (AsPh4)2 [{Fe(‘apS4’)}2] (5) was synthesized and completely characterized [‘apS4’4− = 1,3‐bis(2,3‐dimercaptobenzamido)propane(4−)]. Complex 5 contains two cofacial [FeIII(S2C6H4R)2]− units linked by [Fe−S−Fe] thiolate bridges and two peripheral propanediamide ligand backbones that are located on opposite sides of the molecular anion and prevent the complete separation of the two [FeS4] cores of 5 if the Fe−S−Fe bridges dissociate. No marked differences were found in the molecular parameters, spectroscopic, magnetic and electrochemical properties of the [Fe2S8] cores in the anion of 5 and the parent complex [{Fe(S2C6H4)2}2]2−. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

Sulfur Ligand Substitution at the Nickel(II) Sites of Cubane-Type and Cubanoid NiFe3S4 Clusters Relevant to the C-Clusters of Carbon Monoxide Dehydrogenase

“…Its structure reveals retention of the cubane-type core with the same mean Fe-(μ 3 -S) and terminal Fe−S distances as in 7 (Figure , Table ). The tdt ligand is symmetrically bound to Fe1, which exhibits approximate square pyramidal coordination similar to that in dinuclear Fe III complexes such as [Fe 2 (bdt) 4 ] 2- and [Fe 2 (tdt) 4 ] 2- . − In this description, atoms S1S2S8S9 define the basal plane and S3 is in the axial position. Atom Fe4 is displaced from this plane toward S3 by 0.569(2) Å.…”

Structural control of dithiazolyl radicals: Case studies on 3′- and 4′-cyano-benzo-1,3,2-dithiazolyl, NCC6H3S2N

“…In comparison, reductive deprotection of thiolates to generate dithiols tends to require harsh conditions e.g. Na/l AE NH 3 which may not always support chemically sensitive functional groups [17].…”

Benzene-o-dithiolate ligands as versatile building blocks in supramolecular chemistry

“…A dinuclear double-stranded complex (AsPh 4 ) 2 [Fe 2 (7) 2 ] was obtained which differs significantly from that of the dinuclear nickel complexes. 37 The anion [Fe 2 (7) 2 ] 22 contains two FeS 4 units that are linked by two Fe-S-Fe bridges leading to two distorted square pyramidal, five coordinate iron centres (Fig. 8).…”