Abstract
The effect of tethering a thioether to a rhodium(II) paddlewheel complex are evaluated in Si–H insertion reactions. This study provides further evidence for the benefits of incorporating thioethers into the rhodium paddlewheel motif. When using a tethered complex, the in situ carbenoid formation and subsequent Si–H insertion are not impeded, yields are improved by up to 12 % at elevated temperatures, and selectivity for diazo compounds is greater when compared to non‐tethered catalysts. Computational modelling of the complexes is also presented in order to rationalize the results.
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