Abstract
Despite a recent proposal on the mechanism of a single-electron transfer (SET) process between tritylium and 2,6-bis(diisopropylphenyl)imidazol-2-ylidene (IPr) based on evidence of transient IPr radical cation intermediate ([IPr]⋅+ ) formation, such oxidation is still contentious because of the high oxidation potential of N-heterocyclic carbenes. Our experimental analysis indicates that the appearance of deep purple color, previously considered to be from transient [IPr]⋅+ , originates from a zwitterionic intermediate (3 a), not a radical cation. Here, we propose an alternative mechanism for the reaction involving tritylium and IPr. This mechanism is noteworthy for explaining how [NHC-H]+ can be generated without the formation of transient [NHC]⋅+ , which has been frequently proposed as an intermediate for the reaction between NHC and oxidants. These results also show that a transient strong single-electron donor (3 a) could be generated by the alternative mechanism for oxidants using NHCs, which is a more feasible explanation for the reactivity of NHCs with oxidants.
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