title: Steric modifications tune the regioselectivity of the alkane oxidation catalyzed by non-heme iron complexes.
abstract: Iron complexes with the tetradentate N-donor ligand N,N'-di(phenylmethyl)-N,N'-bis(2-pyridinylmethyl)-1,2-cyclohexanediamine (bbpc) are reported. Despite the benzyl groups present on the amines, the iron compounds catalyze the oxygenation of cyclohexane to an extent similar to those employing less sterically encumbered ligands. The catalytic activity is strongly dependent on the counterion, with the highest activity and the strongest preference for alkane hydroxylation correlating to the most weakly coordinating anion, SbF(6)(-). The selectivity for the alcohol product over the ketone is amplified when acetic acid is present as an additive. When hydrocarbon substrates with both secondary and tertiary carbons are oxidized by H(2)O(2), the catalyst directs oxidation toward the secondary carbons to a greater degree than other previously reported iron-containing homogeneous catalysts.
authors: Department of Chemistry and Biochemistry, Auburn University, Auburn, Alabama 36849, USA.
authors: Yu
authors: Y
authors: He
authors: John D
authors: JD
authors: Gorden
authors: Christian R
authors: CR
authors: Goldsmith
mesh_terms: D000473:Alkanes / Q000737:chemistry*; D001559:Benzhydryl Compounds / Q000737:chemistry*; D002384:Catalysis; D060326:Chemistry Techniques, Synthetic; D056831:Coordination Complexes / Q000737:chemistry*; D018360:Crystallography, X-Ray; D003510:Cyclohexanes / Q000737:chemistry; D003514:Cyclohexylamines / Q000737:chemistry*; D004578:Electron Spin Resonance Spectroscopy; D006861:Hydrogen Peroxide / Q000737:chemistry; D006900:Hydroxylation; D007501:Iron; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D015394:Molecular Structure; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D000473:Alkanes; D001559:Benzhydryl Compounds; D056831:Coordination Complexes; D003510:Cyclohexanes; D003514:Cyclohexylamines; D008024:Ligands; C506365:Cyclohexane; D006861:Hydrogen Peroxide; C030435:1,2-cyclohexanediamine; D007501:Iron; D010100:Oxygen