Daniel Mendoza-Espinosa, Alejandro Alvarez-Hernández, Deyanira Angeles-Beltrán, Guillermo E. Negrón-Silva, Oscar R. Suárez-Castillo, and José M. Vásquez-Pérez,Inorg. Chem., 2017, 56(4), 2092-2099DOI: 10.1021/acs.inorgchem.6b02778
Following a copper catalyzed alkyne azide cycloaddition (CuAAC)and N-alkylation protocols, we report the preparation of a hybrid N-heterocyclic/mesoionic [NHC(H+)-MIC(H+)][2I]2? salt (1) in high yields. The treatment ofsalt 1 with Cu2O and KI yields a second hybrid NHC/MIC proligand featuring atetraiodocuprate anion [NHC(H+)-MIC(H+)][Cu2I4]2? (2). Through selectivedeprotonation and metalation, both salts 1 and 2 can generate either the chelateheterodicarbene complexes (3) with the rare [NHC(M)MIC]+[MX2]? generalformula (M = PdII, RhI) or NHC-anchored/pendent triazolium species (4)[NHC(M)-MIC(H+)]. If the triazolium moiety of type 4 complexes isdeprotonated with KHMDS in the presence of a second metal center, a seriesof heterobimetallic complexes of the type [NHC(M)-MIC(M?)] (5) areachieved. Interestingly, the reaction of salt 2 with KHMDS yields the bimetalliccopper heterodicarbene (6) which can be a useful transfer reagent for the preparation of type 3 complexes. A variety of syntheticroutes for the preparation of complexes 3?5 and their full characterization in solution and in the solid state will be discussed.