700875-33-8Relevant academic research and scientific papers
The reactivity patterns of low-coordinate iron-hydride complexes
Yu, Ying,Sadique, Azwana R.,Smith, Jeremy M.,Dugan, Thomas R.,Cowley, Ryan E.,Brennessel, William W.,Flaschenriem, Christine J.,Bill, Eckhard,Cundari, Thomas R.,Holland, Patrick L.
, p. 6624 - 6638 (2008/12/22)
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 [(β-diketiminate)Fe(μ-H)]2 react rapidly with representative cyanide, isocyanide, alkyne, N2, alkene, diazene, azide, CO2, carbodiimide, and Bronsted 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 H2 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.
Low-Coordinate Iron(II) Amido Complexes of β-Diketiminates: Synthesis, Structure, and Reactivity
Eckert, Nathan A.,Smith, Jeremy M.,Lachicotte, Rene J.,Holland, Patrick L.
, p. 3306 - 3321 (2008/10/09)
The synthesis, structure, and reactivity of a series of low-coordinate Fe(II) diketiminate amido complexes are presented. Complexes L RFeNHAr (R = methyl, tert-butyl; Ar = para-tolyl, 2,6-xylyl, and 2,6-diisopropylphenyl) bind Lewis bases to give trigonal pyramidal and trigonal bipyramidal adducts. In the adducts, crystallographic and 1H NMR evidence supports the existence of agostic interactions in solid and solution states. Complexes LRFeNHAr may be oxidized using AgOTf, and the products LRFe(NHAr)(OTf) are characterized with 19F NMR spectroscopy, UV/vis spectrophotometry, solution magnetic measurements, elemental analysis, and, in one case, X-ray crystallography. In the structures of the iron(III) complexes LRFe(NHAr)(OTf) and L RFe(OtBu)(OTf), the angles at nitrogen and oxygen result from steric effects and not π-bonding. The reactions of the amido group of L RFeNHAr with weak acids (HCCPh and HOtBu) are consistent with a basic nitrogen atom, because the amido group is protonated by terminal alkynes and alcohols to give free H2NAr and three-coordinate acetylide and alkoxide complexes. The trends in complex stability give insight into the relative strength of bonds from three-coordinate iron to anionic C-, N-, and O-donor ligands.
