New class of diiron dithiolates related to the Fe-only hydrogenase active site: synthesis and characterization of [Fe2(SR)(2)(CNMe)7]2+.
Electron-rich polyisocyano derivatives Fe(2)(S(2)C(n)H(2n)(CO)(6-x)(CNMe)(x) (x approximately 4) undergo oxidatively induced (FeCp(2)(+)) reaction with additional CNMe to give [Fe(2)(SR)(2)(CNMe)(7)](PF(6))(2), a new class of iron thiolates. Crystallographic characterization established that the 34 e(-) dinuclear core resembles the oxidized (H(2)-binding) form of the active sites of the Fe-only hydrogenases, key features being the face-sharing bioctahedral geometry, the mu-CX ligand, and an Fe-Fe separation of 2.61 A. Oxidation of the phenylthiolate Fe(2)(SPh)(2)(CO)(2)(CNMe)(4) led to mononuclear [Fe(SPh)(CNMe)(5)](PF(6)), which is analogous to [Fe(2)(SR)(2)(CNMe)(10)](PF(6))(2) formed upon treatment of [Fe(2)(S(2)C(3)H(6))(CNMe)(7)](PF(6))(2) with excess CNMe.
Lawrence
Joshua D
JD
Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA.
Rauchfuss
Thomas B
TB
Wilson
Scott R
SR
D001665:Binding Sites; D002412:Cations / Q000737:chemistry; D018360:Crystallography, X-Ray; D003486:Cyanides / Q000138:chemical synthesis / Q000737:chemistry*; D004563:Electrochemistry; D004578:Electron Spin Resonance Spectroscopy; D005296:Ferrous Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D006864:Hydrogenase / Q000737:chemistry*; D007506:Iron-Sulfur Proteins / Q000737:chemistry*; D008024:Ligands; D008968:Molecular Conformation; D010084:Oxidation-Reduction; D013457:Sulfur Compounds / Q000737:chemistry*
D002412:Cations; D003486:Cyanides; D005296:Ferrous Compounds; D007506:Iron-Sulfur Proteins; D008024:Ligands; D013457:Sulfur Compounds; C118830:iron hydrogenase; D006864:Hydrogenase