Kirk, Ryan M.Hill, Anthony F.2025-12-162025-12-161433-7851WOS:001493597300001ORCID:/0000-0003-2167-0604/work/186563762https://hdl.handle.net/1885/733795459Phosphinoisocyanide complexes undergo facile [3 + 2] cycloaddition reactions with activated alkynes to afford the first azaphospholylidene complexes which are rare examples of N,P-heterocyclic carbenes (NPHC). In addition to quantifying the donor/acceptor properties of this new class of carbene, their transmetalation reactions are also described.The authors gratefully acknowledge the Australian Research Council (DP230100215) for funding.6en© 2025 The Author(s). Angewandte Chemie International Edition published by Wiley-VCH GmbH.CycloadditionHeterocyclic carbeneIsocyanidePhosphorus heterocyclesTransmetalation202510.1002/anie.202504620105006610923