title: Synthesis, characterization, and dioxygen reactivity of tetracarboxylate-bridged Diiron(II) complexes with coordinated substrates.
abstract: The synthesis and characterization of [Fe(2)(micro-O(2)CAr(Tol))(4)L(2)] complexes, where L is benzylamine or 4-methoxybenzylamine (BA(p)()(-)(OMe)), are described. The reaction of the latter diiron(II) complex with dioxygen at -78 degrees C affords a metastable mixed-valent Fe(II)Fe(III) green intermediate. When O(2) is introduced at ambient temperature, N-dealkyation occurs to yield anisaldehyde, eliminating N-oxidation as a viable pathway for the reaction. Use of [Fe(2)(micro-O(2)CAr(T)(omicron)(l))(4)(alpha-d(1)-BA(p)()(-)(OMe))(2)] allowed a deuterium kinetic isotope of approximately 3 to be determined.
authors.affiliation: Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
authors.forename: Sungho
authors.initials: S
authors.lastname: Yoon
authors.forename: Stephen J
authors.initials: SJ
authors.lastname: Lippard
mesh_terms: D001596:Benzylamines / Q000138:chemical synthesis / Q000737:chemistry* / Q000378:metabolism; D040761:Biomimetic Materials / Q000138:chemical synthesis / Q000737:chemistry / Q000378:metabolism; D002264:Carboxylic Acids / Q000138:chemical synthesis / Q000737:chemistry / Q000378:metabolism; D018360:Crystallography, X-Ray; D058085:Iron Compounds / Q000138:chemical synthesis / Q000737:chemistry* / Q000378:metabolism; D006899:Mixed Function Oxygenases / Q000737:chemistry* / Q000378:metabolism; D010100:Oxygen / Q000737:chemistry* / Q000378:metabolism
chemical_list: D001596:Benzylamines; D002264:Carboxylic Acids; D058085:Iron Compounds; D006899:Mixed Function Oxygenases; D010100:Oxygen