Pushing the limits of neutral organic electron donors : A tetra(iminophosphorano)-substituted bispyridinylidene

Hanson, Samuel S. and Doni, Eswararao and Traboulsee, Kyle T. and Coulthard, Graeme and Murphy, John A. and Dyker, C. Adam (2015) Pushing the limits of neutral organic electron donors : A tetra(iminophosphorano)-substituted bispyridinylidene. Angewandte Chemie International Edition, 54 (38). pp. 11236-11239. ISSN 1433-7851

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    Abstract

    A new ground-state organic electron donor has been prepared that features four strongly π-donating iminophosphorano substituents on a bispyridinylidene skeleton. Cyclic voltammetry reveals a record redox potential of −1.70 V vs. saturated calomel electrode (SCE) for the couple involving the neutral organic donor and its dication. This highly reducing organic compound can be isolated (44 %) or more conveniently generated in situ by a deprotonation reaction involving its readily prepared pyridinium ion precursor. This donor is able to reduce a variety of aryl halides, and, owing to its redox potential, was found to be the first organic donor to be effective in the thermally induced reductive S[BOND]N bond cleavage of N,N-dialkylsulfonamides, and reductive hydrodecyanation of malonitriles.