Synthesis and Mössbauer characterization of octahedral iron(II) carbonyl complexes FeI2(CO)3L and FeI2(CO)2L2: developing models of the [Fe]-H(2)ase active site.
A series of mono- and disubstituted complexes, FeI(2)(CO)(x)L(4-x), x = 2 or 3, is conveniently accessed from simple mixing of N-heterocyclic carbenes, phosphines, and aromatic amines with FeI(2)(CO)(4), first reported by Hieber in 1928. The highly light sensitive complexes yield to crystallization and X-ray diffraction studies for six complexes showing them to be rudimentary structural models of the monoiron hydrogenase, [Fe]-H(2)ase or Hmd, active site in native (Fe(II)(CO)(2)) or CO-inhibited (Fe(II)(CO)(3)) states. Diatomic ligand (nu(CO)) vibrational and Mossbauer spectroscopies are related to those reported for the Hmd active site. The importance of a serial approach for relating such parameters in model compounds to low spin Fe(II) in the diverse ligation of enzyme active sites is stressed.
Department of Chemistry, Texas A&M University, College Station, Texas 77843, USA.
Bin
B
Li
Tianbiao
T
Liu
Codrina V
CV
Popescu
Andrey
A
Bilko
Marcetta Y
MY
Darensbourg
D002248:Carbon Monoxide / Q000737:chemistry*; D020134:Catalytic Domain; D018360:Crystallography, X-Ray; D005296:Ferrous Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D006864:Hydrogenase / Q000737:chemistry* / Q000378:metabolism; D007506:Iron-Sulfur Proteins / Q000737:chemistry* / Q000378:metabolism; D008024:Ligands; D008958:Models, Molecular; D008968:Molecular Conformation; D015204:Spectroscopy, Mossbauer
D005296:Ferrous Compounds; D007506:Iron-Sulfur Proteins; D008024:Ligands; D002248:Carbon Monoxide; C118830:iron hydrogenase; D006864:Hydrogenase