Highest recorded N-O stretching frequency for 6-coordinate {Fe-NO}7 complexes: an iron nitrosyl model for His3 active sites.
We report the synthesis, structure, and reactivity of [Fe(T1Et4iPrIP)(OTf)2] [1; T1Et4iPrIP = tris(1-ethyl-4-isopropylimidazolyl)phosphine]. Compound 1 reacts reversibly with nitric oxide to afford [Fe(T1Et4iPrIP)(NO)(THF)(OTf)](OTf) (2), which is the first example of a 6-coordinate {FeNO}(7) S = 3/2 complex containing a linear Fe-N-O group. 2 exhibits the highest ν(NO) for compounds in this class. Density functional theory studies reveal an enhanced degree of β-electron transfer from π*(NO) to the Fe d orbitals accounting for the large stretching frequency.
Department of Chemistry, Oakland University , Rochester, Michigan 48309-4477, United States.
Jia
J
Li
Atanu
A
Banerjee
Piotr L
PL
Pawlak
William W
WW
Brennessel
Ferman A
FA
Chavez
D001665:Binding Sites; D049308:Dioxygenases / Q000737:chemistry / Q000378:metabolism*; D005290:Ferric Compounds / Q000737:chemistry*; D006860:Hydrogen Bonding; D007501:Iron / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D009584:Nitrogen / Q000737:chemistry*; D009589:Nitrogen Oxides / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry*
D005290:Ferric Compounds; D009589:Nitrogen Oxides; C073661:dinitrosyl iron complex; D007501:Iron; D049308:Dioxygenases; D009584:Nitrogen; D010100:Oxygen