New horizons in organic electron transfer

The aim of this project was to explore the scope of electron transfer reactions from organic electron donors, that had been first discovered by us in 2005. This grant provided the foundation for important advances in our work that are still developing further some 7 years later. It led to publcations in the highest profile journals in chemistry.

This work led to important advances including publication of the first neutral ground-state organic electron donor (an imidazole-derived donor) that reduced iodoarenes to aryl anions (published in Angew. Chem. Int. Ed)., the reductive cleavage of activated arenesulfonamides and gem-bis-sulfones (J. Am. Chem. Soc.). It also led to a novel DMAP-derived electron donor of equal potency that did all of the above reactions as well as reduction of Weinreb amides and acyloin derivatives. This new donor was very easy to synthesise (in contrast to the previous donor). With both donors, we demonstrated that they were 2-electron donors to iodoarenes and that when they led to alkyl radicals, that these radicals were efficiently trapped by the radical cations of the donors (J. Am. Chem. Soc. and OBC). The synthesis of the imidazole-derived donor led to a by-product that easily complexed metal ions, nickel (J. Am. Chem. Soc.) and cobalt as 'crown carbenes' that themseleves functioned as very strong electron donors. Finally the project led to the preparation of hyvrid donors that shed light on the reactivity of these novel compounds.