Investigations into the reactivity, properties, and applications of Os(aryl)4 complexes have been hampered by their low yielding syntheses from volatile and toxic OsO4 (typically ≤34%). We have recently found that air-stable M(aryl)4 compounds (M = Os, Ru) can be prepared in good yields up to 76% starting from new, less hazardous (Oct4N)2[MX6] precursors (M = Os, Ru; X = Cl, Br). This approach avoids the formation of osmium oxoaryl side products, facilitating the preparation of complexes comprising bulky 2,6-methyl substituted aryl ligands for the first time. We are currently developing new synthetic routes to access functionalized Os(aryl)4 compounds, and studying how substituents influence their solid-state structure and redox properties. Through explorations of their reaction chemistry and fundamental properties, we hope to increase the utility of this relatively underexplored class of organometallic complexes in established and emerging areas of molecular materials science.

Metal(IV) tetraaryl complexes

ACS Spring Meeting 2021

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