title: The reactivity patterns of low-coordinate iron-hydride complexes.
abstract: We report a survey of the reactivity of the first isolable iron-hydride complexes with a coordination number less than 5. The high-spin iron(II) complexes [(beta-diketiminate)Fe(mu-H)] 2 react rapidly with representative cyanide, isocyanide, alkyne, N 2, alkene, diazene, azide, CO 2, carbodiimide, and Brønsted acid containing substrates. The reaction outcomes fall into three categories: (1) addition of Fe-H across a multiple bond of the substrate, (2) reductive elimination of H 2 to form iron(I) products, and (3) protonation of the hydride to form iron(II) products. The products include imide, isocyanide, vinyl, alkyl, azide, triazenido, benzo[ c]cinnoline, amidinate, formate, and hydroxo complexes. These results expand the range of known bond transformations at iron complexes. Additionally, they give insight into the elementary transformations that may be possible at the iron-molybdenum cofactor of nitrogenases, which may have hydride ligands on high-spin, low-coordinate metal atoms.
authors.affiliation: Department of Chemistry, University of Rochester, Rochester, New York, 14627, USA.
authors.forename: Ying
authors.initials: Y
authors.lastname: Yu
authors.forename: Azwana R
authors.initials: AR
authors.lastname: Sadique
authors.forename: Jeremy M
authors.initials: JM
authors.lastname: Smith
authors.forename: Thomas R
authors.initials: TR
authors.lastname: Dugan
authors.forename: Ryan E
authors.initials: RE
authors.lastname: Cowley
authors.forename: William W
authors.initials: WW
authors.lastname: Brennessel
authors.forename: Christine J
authors.initials: CJ
authors.lastname: Flaschenriem
authors.forename: Eckhard
authors.initials: E
authors.lastname: Bill
authors.forename: Thomas R
authors.initials: TR
authors.lastname: Cundari
authors.forename: Patrick L
authors.initials: PL
authors.lastname: Holland
mesh_terms: D000480:Alkynes / Q000737:chemistry; D002248:Carbon Monoxide / Q000737:chemistry; D003486:Cyanides / Q000737:chemistry; D005296:Ferrous Compounds / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy / Q000379:methods; D008983:Molybdoferredoxin / Q000737:chemistry; D009584:Nitrogen / Q000737:chemistry; D010088:Oxidoreductases / Q000737:chemistry; D015204:Spectroscopy, Mossbauer; D014961:X-Ray Diffraction
chemical_list: D000480:Alkynes; D003486:Cyanides; D005296:Ferrous Compounds; D008983:Molybdoferredoxin; D002248:Carbon Monoxide; D006859:Hydrogen; D010088:Oxidoreductases; C029130:nitrogenase reductase; D009584:Nitrogen