Metal-metal bonded diruthenium paddlewheel complexes are currently of interest for their applications in oxidative catalysis. Our recent efforts with diruthenium compounds have focused on stabilizing elusive, high oxidation state intermediate species to determine how the electronic structure affects their reactivity. Here we present a systematic series of new Ru26+ compounds, prepared via one-electron oxidation of their Ru25+ precursors, that are supported by anilinopyridinate ligands decorated with electron-donor groups. Of note, most previously reported Ru26+ compounds contain strongly sigma-donating axial ligands that induce a diamagnetic ground state, while our complexes contain pi-donor halide ligands and are instead intermediate spin, S = 1. These compounds have been studied using X-ray crystallography, SQUID magnetometry, NMR spectroscopy, magnetic circular dichroism, and electrochemistry. The experimental results are further supported with DFT calculations, which, in combination with the electrochemical experiments, provide a preliminary explanation for why subsequent oxidation to Ru27+ is not readily observed.

Exploring the electronic structure of novel Ru26+ paddlewheel complexes

ACS Spring Meeting 2021

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