Electron donors with unprecedented power can unlock many new and important chemical and catalytic processes. In synthesis, electron transfer reactions using organic “super-electron-donors” promote radical intermediates for chemical substitutions, additions, cyclizations, polymerizations, and cascade processes for formation of polycyclic carbon skeletons. In catalysis, multiple electron transfers from strong donors produce fuels and other more complex molecules from simple feedstocks. The inherently most powerful neutral-molecule electron donors yet known are the dimetal tetraguanidinate complexes. The Mo2 and W2 tetraguanidinate paddlewheel complexes were studied as electrocatalysts for the production of hydrogen from weak acids. It was found that the Lewis base sites of the guanidinate ligands and the Lewis acid axial sites of the Mo complex form a frustrated Lewis pair that works together synergistically to enable protonation at the nucleophilic guanidinate site with acetate coordination to the electrophilic Mo2 axial site, but electrocatalysis was not observed. By moving to the stronger electron-donating W2 core, electrocatalytic production of hydrogen was achieved. The catalytic mechanism and performance will be presented.

Super-electron-donor dimetal complexes acting as frustrated Lewis pairs: Electrocatalytic production of hydrogen from weak acids

2019 Spring National Meeting

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