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Oxidative Generation of Boron-Centered Radicals in Carboranes

preprint
submitted on 22.12.2019, 05:55 and posted on 23.12.2019, 22:37 by Harrison A. Mills, Joshua Martin, Arnold L. Rheingold, Alexander Spokoyny

We report the first indirect observation and use of boron vertex-centered carboranyl radicals generated by the oxidation of modified carboranyl precursors. These radical intermediates are formed by the direct oxidation of a B−B bond between a boron cluster cage and an exopolyhedral boron-based substituent (e.g., −BF3K, −B(OH)2). The in situ generated radical species are shown to be competent substrates in reactions with oxygen-based radicals, dichalcogenides, and N-heterocycles, yielding the corresponding substituted carboranes containing B−O, B−S, B−Se, B−Te, and B−C bonds. Remarkably, this chemistry tolerates various electronic environments, providing access to facile substitution chemistry at both electron-rich and electron-poor B−H vertices in carboranes.

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in Journal of the American Chemical Society

ChemRxiv

Funding

NIGMS R35GM124746

History

Email Address of Submitting Author

spokoyny@chem.ucla.edu

Institution

UCLA

Country

USA

ORCID For Submitting Author

0000-0002-5683-6240

Declaration of Conflict of Interest

Authors declare no conflicts of interest.

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Read the published paper

in Journal of the American Chemical Society

ChemRxiv

Exports