The reactivity patterns of low-coordinate iron-hydride complexes.
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.
Yu
Ying
Y
Department of Chemistry, University of Rochester, Rochester, New York, 14627, USA.
Sadique
Azwana R
AR
Smith
Jeremy M
JM
Dugan
Thomas R
TR
Cowley
Ryan E
RE
Brennessel
William W
WW
Flaschenriem
Christine J
CJ
Bill
Eckhard
E
Cundari
Thomas R
TR
Holland
Patrick L
PL
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
D000480:Alkynes; D003486:Cyanides; D005296:Ferrous Compounds; D008983:Molybdoferredoxin; D002248:Carbon Monoxide; D006859:Hydrogen; D010088:Oxidoreductases; C029130:nitrogenase reductase; D009584:Nitrogen