A Capable Bridging Ligand for Fe-Only Hydrogenase:  Density Functional Calculations of a Low-Energy Route for Heterolytic Cleavage and Formation of Dihydrogen

Spin distribution of the H-cluster in the Hox–CO state of the [FeFe] hydrogenase from Desulfovibrio desulfuricans: HYSCORE and ENDOR study of 14N and 13C nuclear interactions

“…Reanalysis of the X-ray crystallographic structure together with some theoretical studies have proposed a -CH 2 -NH-CH 2 -moiety for the bridging dithiol ligand in the binuclear subcluster (Structure 1) [20,60]. Therefore, the observed 14 N signals could also originate from this ligand, though it seems unlikely, owing to its remote position with respect to the iron atoms.…”

The roles of the first and second coordination spheres in the design of molecular catalysts for H2production and oxidation

“…1,9,10 In this reaction, H 2 binds to the distal iron atom (Fe d ) in the first step to form a dihydrogen complex. This is followed by heterolytic cleavage of hydrogen in step 2 to produce an iron hydride and a protonated amine.…”

Metal–ligand cooperation by aromatization–dearomatization as a tool in single bond activation

“…However, there are classes of catalysts in chemical and biological processes in which the ligands can cooperate with the metal centre by jointly interacting with the substrate and undergoing reversible bond-making and -breaking processes during substrate activation and product formation [1][2][3]. For example, metal-ligand cooperation (MLC) between an amine ligand and an iron centre is thought to be involved in the catalytic mechanism of the enzyme hydrogenase [4]. MLC involving metal-amido metal-amine transformations (scheme 1) [5,6] takes place in catalytic hydrogenation of polar double bonds [6][7][8][9][10].…”