Structural Conversions of Synthetic and Protein-Bound Iron–Sulfur Clusters

Abstract

Synthetic iron-sulfur clusters of general formulation [FeSL] with core atoms Fe and S and terminal ligands L constitute a family of molecular clusters with remarkably diverse geometrical and electronic structures. Several structure types are also found in proteins. The large majority of research on these clusters has involved elucidation of physical properties. Here, we direct attention to reactivity in the form of cluster conversions in which the FeS cores of reactants are transformed to new structures, usually of different nuclearity, in overall reactions such as self-assembly and fragment condensation and dissociation. An extensive body of core conversions, many of which have not been recognized as such, are presented including those in biological systems. All structural core types are depicted, and all core conversions are diagrammatically summarized. Clusters containing the cubane-type FeS core play a central role in conversion chemistry. The core conversion concept tends to reinforce the description of iron-sulfur cores as modular units subject to various covalent bond interactions that lead to different structures.

Evolutionary Relationships Between Low Potential Ferredoxin and Flavodoxin Electron Carriers

“…Low potential PECs differ in their iron requirements and stabilities in the presence of atmospheric O 2 concentrations (Jagannathan et al, 2012;Pierella Karlusich et al, 2014;Holm and Lo, 2016). To determine if an organism's environmental niche correlates with PEC abundance, we evaluated how an organism's preferences for O 2 , external pH, and temperature relate to the average number of PEC genes found in a genome.…”

Energy storage inspired by nature – ionic liquid iron–sulfur clusters as electrolytes for redox flow batteries

“…So far this differing behavior in the flow cell remains unaccounted, but is further investigated. This flexibility of iron-sulfur cluster structures prevents actual decomposition especially since [Fe 4 S 4 (Stfe) 4 ] 2− is known to be a thermodynamic sink in iron-sulfur-thiolate chemistry 50,58,59 and thus can be reformed.…”

Construction of a Planar Tetrapalladium Cluster by the Reaction of Palladium(0) Bis(isocyanide) with Cyclic Tetrasilane

“…The remaining powder was washed with HMDSO (5 mL × 2) to afford 5 as a brown powder (50 mg, 0.038 mmol, 63%). Crystals suitable for X-ray diffraction analysis were obtained by cooling the saturated pentane solution at −35 • C. 1 (6) In a 20-mL Schlenk tube, 4 (30 mg, 0.027 mmol) was dissolved in benzene (20 mL), then trimethylolpropane phosphite (31 mg, 0.19 mmol) was added to this solution at room temperature. The solution was stirred at room temperature for 1 h. After freeze-drying, the remaining solid was dissolved in ether (20 mL), and centrifuged to remove the insoluble materials.…”

“…Detailed spectroscopic analysis of the substrates coordinated to the cluster framework has provided unique insight into the function of the active surface in, for example, the chemisorption process [4,5]. Moreover, some of the clusters provide structural and/or functional mimics of the active sites in enzymes [6][7][8][9]. A typical way to prepare the clusters is the self-assembly of metals and bridging ligands, by simply mixing the appropriate metal precursors in proper molar ratios under suitable reaction conditions.…”