Oxidation of sulfide, phosphine, and benzyl substrates tethered to N-donor pyridine ligands in carboxylate-bridged diiron(II) complexes.
Substituted pyridines were employed to prepare a series of terphenylcarboxylate-bridged diiron(II) compounds to mimic aspects of the chemistry at the active sites of bacterial multicomponent monooxygenases, including soluble methane monooxygenase (sMMO) and toluene monooxygenase (ToMO). Complexes of general formula [Fe2(O2CArTol)4L], L = 2, 3, or 4-pyridyldiphenylphosphine, 2-pyridylphenylsulfide, or 2-benzylpyridine and ArTol = 2,6-di(p-tolyl)benzoate, were synthesized and characterized by X-ray crystallography. Upon exposure of these compounds to dioxygen, ligand oxidation ensued and, in one case, proceeded catalytically.
Carson
Emily C
EC
Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02319, USA.
Lippard
Stephen J
SJ
D001593:Benzyl Compounds / Q000737:chemistry*; D040761:Biomimetic Materials / Q000138:chemical synthesis / Q000737:chemistry; D018360:Crystallography, X-Ray; D005296:Ferrous Compounds / Q000737:chemistry*; D008024:Ligands; D006899:Mixed Function Oxygenases / Q000737:chemistry; D015394:Molecular Structure; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D010720:Phosphines / Q000737:chemistry*; D011725:Pyridines / Q000737:chemistry*; D013440:Sulfides / Q000737:chemistry*
D001593:Benzyl Compounds; D005296:Ferrous Compounds; D008024:Ligands; D010720:Phosphines; D011725:Pyridines; D013440:Sulfides; D006899:Mixed Function Oxygenases; D010100:Oxygen