Bio-inspired nonheme iron catalysts have been shown to catalyze oxidation of inert C–H and C=C bonds. They can be divided into two groups - one forming an electrophilic oxidant and the other forming a nucleophilic oxidant. [Fe(β-BPMCN)]2+ and [Fe(β-BQCN)]2+ (where BPMCN = N,N’-bis(2-pyridylmethyl)-N,N’-dimethyl-trans-1,2-diaminocyclohexane and BQCN = N,N’-bis(8-quinolyl)-N,N’-dimethyl-trans-1,2-diaminocyclohexane) fall into the latter category and in their reactions with hydrogen peroxide form nucleophilic oxidants that favor electron-deficient olefins in competitive C=C oxidations involving both electron-deficient and electron-rich olefins. Quite interestingly, for both of these systems in the presence of acetic acid, the oxidants become electrophilic favoring oxidation of electron-rich olefins. However, the effect of this change on the electronic nature of the active oxidant in case of C–H bond hydroxylation has yet to be determined. Taking advantage of the observation that both electrophilic and nucleophilic oxidants can be formed using the same ligand frameworks under different conditions, we are evaluating the effects of the electronic nature of the oxidant on alkane hydroxylation.

Bio-inspired nonheme iron catalyst: Electrophilic versus nucleophilic iron-based active oxidant – effect on alkane hydroxylation

253rd National Meeting (2017)

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