The Third Hydrogenase: A Ferracyclic Carbamoyl with Close Structural Analogy to the Active Site of Hmd

Biomimetic Hydrogenation Catalyzed by a Manganese Model of [Fe]‐Hydrogenase

“…Two Fe models supported by an anthracene‐bridged NCS ligand could also activate H 2 . Notably these two models contained a carbamoyl donor, instead of the acyl donor found in the enzyme. Among them, the neutral derivative 3 (Figure d) mediated the hydrogenation of 2,6‐difluoro(phenyl)‐2‐(4‐ethyl)imidazolium cation, a model of methenyl‐H 4 MPT + .…”

A Five‐Coordinate Iron Center in the Active Site of [Fe]‐Hydrogenase: Hints from a Model Study

“…[7,14] A number of smallmolecule mimics of [Fe]-hydrogenase have been reported. [15][16][17][18][19][20][21][22][23][24][25] To date, all of the advanced models that contain iron acyl or carbamoyl moieties [17,19,20,23,24] are sixcoordinate. Herein we describe the synthesis, structure, and reactivity of the first five-coordinate model complex reproducing the coordination sphere of the Fe ion in [Fe]-hydrogenase.…”

“…The thermal ellipsoids are displayed at 50 % probability. Selected bond lengths [] and angles[8]: Fe1-N1 2.002(3), Fe1-S1 2.2163(12), Fe1-C11 1.915(5), Fe1-C1 1.773(5), Fe1-C2 1.786(5), C1-O1 1.155(5), C2-O2 1.144(5), C11-O7 1.209(5); C11-Fe1-N1 85.26(17), C1-Fe1-N1 177.08…”

Isocyanides inhibit [Fe]-hydrogenase with very high affinity

“…1) [7]. Recently, several model compounds of FeGP cofactor have been synthesized [22,[29][30][31][32][33]. In some model compounds, an additional ligand, such as CO, cyanide, or isocyanide can bind to the iron site trans to the acyl ligand [22,31,33].…”