title: Catalytic hydrogen evolution by Fe(II) carbonyls featuring a dithiolate and a chelating phosphine.
abstract: Two pentacoordinate mononuclear iron carbonyls of the form (bdt)Fe(CO)P2 [bdt = benzene-1,2-dithiolate; P2 = 1,1'-diphenylphosphinoferrocene (1) or methyl-2-{bis(diphenylphosphinomethyl)amino}acetate (2)] were prepared as functional, biomimetic models for the distal iron (Fe(d)) of the active site of [FeFe]-hydrogenase. X-ray crystal structures of the complexes reveal that, despite similar ν(CO) stretching band frequencies, the two complexes have different coordination geometries. In X-ray crystal structures, the iron center of 1 is in a distorted trigonal bipyramidal arrangement, and that of 2 is in a distorted square pyramidal geometry. Electrochemical investigation shows that both complexes catalyze electrochemical proton reduction from acetic acid at mild overpotential, 0.17 and 0.38 V for 1 and 2, respectively. Although coordinatively unsaturated, the complexes display only weak, reversible binding affinity toward CO (1 bar). However, ligand centered protonation by the strong acid, HBF4·OEt2, triggers quantitative CO uptake by 1 to form a dicarbonyl analogue [1(H)-CO](+) that can be reversibly converted back to 1 by deprotonation using NEt3. Both crystallographically determined distances within the bdt ligand and density functional theory calculations suggest that the iron centers in both 1 and 2 are partially reduced at the expense of partial oxidation of the bdt ligand. Ligand protonation interrupts this extensive electronic delocalization between the Fe and bdt making 1(H)(+) susceptible to external CO binding.
authors.affiliation: Department of Chemistry and Biochemistry and ‡Center for Bio-Inspired Solar Fuel Production, Arizona State University , Tempe, Arizona 85287, United States.
authors.forename: Souvik
authors.initials: S
authors.lastname: Roy
authors.forename: Shobeir K S
authors.initials: SK
authors.lastname: Mazinani
authors.forename: Thomas L
authors.initials: TL
authors.lastname: Groy
authors.forename: Lu
authors.initials: L
authors.lastname: Gan
authors.forename: Pilarisetty
authors.initials: P
authors.lastname: Tarakeshwar
authors.forename: Vladimiro
authors.initials: V
authors.lastname: Mujica
authors.forename: Anne K
authors.initials: AK
authors.lastname: Jones
mesh_terms: D002384:Catalysis; D002614:Chelating Agents / Q000737:chemistry*; D005296:Ferrous Compounds / Q000737:chemistry*; D007659:Ketones / Q000737:chemistry*; D010720:Phosphines / Q000737:chemistry*; D013438:Sulfhydryl Compounds / Q000737:chemistry*
chemical_list: D002614:Chelating Agents; D005296:Ferrous Compounds; D007659:Ketones; D010720:Phosphines; D013438:Sulfhydryl Compounds; C044646:phosphine