Pushing the Limits of Neutral Organic Electron Donors: A Tetra(iminophosphorano)-Substituted Bispyridinylidene

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N bond cleavage of N,N‐dialkylsulfonamides, and reductive hydrodecyanation of malonitriles. Unlocking max potential: The four strongly π‐donating iminophosphorano substituents of compound 1 impart an impressive redox potential of −1.70 V versus the saturated calomel electrode (SCE) for the 12+/1 redox couple, and make 1 the first organic donor able to reduce malononitriles and dialkylarenesulfonamides without photoexcitation.