An iridium N-heterocyclic carbene (NHC) complex with a rare hydrogen wing tip was obtained Via C-N bond cleaVage. The C-bound to N-bound tautomerization of this carbene cannot be achieVed in this neutral 18-electron Ir(III) complex. Chloride abstraction in MeCN afforded an NHCacetimidamide complex, where the N-bound to C-bound tautomerization of this carbene was obserVed in CDCl 3 at 110 °C. Crystal structures of iridium complexes with these rare ligands were reported.
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