title: On the mechanism of iron(III)-dependent oxidative dehydrogenation of amines.
abstract: Kinetic and structural data are presented for the iron-promoted dehydrogenation of the amine, [Fe(III)L3]3+ (1), L3 = 1,9-bis(2'-pyridyl)-5-[(ethoxy-2''-pyridyl)methyl]-2,5,8-triazanonane. Spectroscopic and electrochemical experiments under the exclusion of dioxygen helped to identify reaction intermediates and the final product, the Fe(II)-monoimine complex [Fe(II)L4]2+ (2), L4 = 1,9-bis(2'-pyridyl)-5-[(ethoxy-2''-pyridyl)methyl]-2,5,8-triazanon-1-ene. 2 is formed by disproportionation of the starting complex 1 by a three-step reaction mechanism, most likely via ligand-centered radical intermediates. The rate law can be described by the second-order rate equation, -d[(Fe(III)L3)3+]/dt = k(EtO)- [(Fe(III)L3)3+][EtO-], with k(EtO)- = 4.92 +/- 0.01 x 104 M(-1) s(-1) (60 degrees C, mu = 0.01 M). The detection of general base catalysis and a primary kinetic isotope effect (k(EtO)-(H)/k(EtO)-(D) = 1.73) represents the first kinetic demonstration that the deprotonation becomes rate determining followed by electron transfer in the oxidative dehydrogenation mechanism. We also isolated the Fe(II)-monoimine complex 2 and determined its structure in solution (NMR) and in the solid state (X-ray).
authors.affiliation: Departamento de Química Inorgánica y Nuclear, Facultad de Química, Universidad Nacional Autónoma de México, Ciudad Universitaria, México, DF 04510, México.
authors.forename: Juan Pablo
authors.initials: JP
authors.lastname: Saucedo-Vázquez
authors.forename: Víctor Manuel
authors.initials: VM
authors.lastname: Ugalde-Saldívar
authors.forename: Alfredo Rubén
authors.initials: AR
authors.lastname: Toscano
authors.forename: Peter M H
authors.initials: PM
authors.lastname: Kroneck
authors.forename: Martha Elena
authors.initials: ME
authors.lastname: Sosa-Torres
mesh_terms: D000588:Amines / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D007501:Iron / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D015394:Molecular Structure; D010084:Oxidation-Reduction; D013053:Spectrophotometry
chemical_list: D000588:Amines; D006859:Hydrogen; D007501:Iron