In this work, we characterize the functional group compatibility, rates and positional selectivity of H/D exchange between C-H bonds of 34 substituted (hetero)arenes and TFE-d1 catalyzed by a Pt(II) sulfonated CNN-pincer complex 1 at 80 oC. A thorough investigation into the early phases of the catalytic reaction allowed for the measurement of initial rates for non-equivalent C-H bonds. For N,N-dimethylaniline, nitrobenzene and indole, a moderate to high degree of positional selectivity for the H/D exchange was observed. Due to the lack of correlation between our experimental results and classic Hammett constants σX, a novel set of empirically derived Hammett constants, σXM, for metal-assisted C-H cleavage were developed which may be useful in benchmarking the reactivity of other systems involving metal-assisted C-H activation in arenes.

Rates and selectivity of H/D exchange between (hetero)arenes and 2,2,2-trifluoroethanol-d1 catalyzed by a Pt(II) CNN-pincer complex

ACS Spring Meeting 2021

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