title: Dinuclear iron isonitrile complexes: models for the iron hydrogenase active site.
abstract: Reaction of Fe(2)(mu-S(2)C(3)H(6))(CO)(6) (1) with 2 equiv of t-BuNC affords a disubstitued species Fe(2)(mu-S(2)C(3)H(6))(CN-t-Bu)(2)(CO)(4) (2). The structure of 2 has been determined by X-ray crystallography, which shows that in the solid state both isonitrile ligands are cis to sulfur. In solution, NMR and IR spectroscopy suggest that multiple isomers are present. Protonation of 2 occurs at the Fe-Fe bond to give a cationic complex 3 as four different isomeric species. Complex 3 does not react with deuterium gas (98 psi) in the absence of light. Irradiation of solutions of 3 with visible light under D(2) gas leads to formation of HD.
authors.affiliation: Department of Chemistry, University of Washington, Box 351700, Seattle, Washington 98195-1700, USA.
authors.forename: Jennifer L
authors.initials: JL
authors.lastname: Nehring
authors.forename: D Michael
authors.initials: DM
authors.lastname: Heinekey
mesh_terms: D018360:Crystallography, X-Ray; D003903:Deuterium / Q000737:chemistry; D006864:Hydrogenase / Q000737:chemistry*; D007202:Indicators and Reagents; D007506:Iron-Sulfur Proteins / Q000737:chemistry*; D007536:Isomerism; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy; D008752:Methylene Chloride; D008958:Models, Molecular; D008968:Molecular Conformation; D009570:Nitriles / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D011522:Protons; D013055:Spectrophotometry, Infrared
chemical_list: D007202:Indicators and Reagents; D007506:Iron-Sulfur Proteins; D008024:Ligands; D009570:Nitriles; D009942:Organometallic Compounds; D011522:Protons; D008752:Methylene Chloride; D003903:Deuterium; C118830:iron hydrogenase; D006864:Hydrogenase