Reduced nickel(II)- and cobalt(II)-salen compounds can catalytically reduce alkyl halides.  These reactions have environmental significance, as effective reduction of halogenated organic substrates facilitates conversion of harmful herbicides and fungicides to more benign materials.  Computational chemistry methods are used to characterize the two processes involved � reduction of metal(II)-salens and reaction of reduced metal-salens with alkyl halides � not only for nickel(II)- and cobalt(II)-salen, but a wide range of metal-salens.  In order to establish a means of predicting reduction potentials for metal-salen compounds, electron affinities for a training set of metal-salens were calculated using DFT and correlated with experimental Epc values measured using cyclic voltammetry.  The correlation was applied to the prediction of reduction potentials for a test set of metal-salens, including those with aliphatic and aromatic bridging groups.  Second, the thermodynamics of the reaction of reduced forms of metal-salens with a variety of alkyl halides is determined using additional DFT calculations.

Prediction of reduction potentials from electron affinities for metal-salens  and application to the reduction of alkyl halides

239th National Meeting (2010)

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