In our effort to develop more environmentally friendly alternatives to osmium-catalyzed olefin cis-dihydroxylation, we have been investigating the catalytic activities of iron(II) complexes supported by tetradentate N4 ligands with H2O2 as an economical and atom-efficient oxidant. Towards this end, we have found that the iron(II) complex of bis(2-quinolinylmethyl)-6-methyl-pyridyl-2-methylamine (6-MeBQPA) can catalyze the cis-dihydroxylation of 1-octene with high conversion of the H2O2 into the diol product. Furthermore, unlike the iron(II) complex of the parent tris(pyridyl-2-methyl)amine ligand, the 6-MeBQPA complex does not catalyze facile disproportionation of H2O2, permitting us for the first time to conduct detailed kinetic studies for this class of catalyst. These kinetic studies will be presented, as well as the effects of additives such as chloride, 3-nitrobenzoic acid, and urea. Our results suggest that the reaction proceeds by rapid formation of an Fe(II)/H2O2 adduct followed by rate determining O-O bond cleavage to form an Fe(IV)(OH)2 oxidant.

Nonheme iron-catalyzed olefin cis-dihydroxylation: Kinetics and the effects of additives

243rd National Meeting (2012)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.