Bridged N?Heterocyclic/Mesoionic (NHC/MIC) Heterodicarbenes as Ligands for Transition Metal Complexes. Daniel Mendoza-Espinosa, Alejandro Alvarez-Herna?ndez, Deyanira Angeles-Beltra?n, Guillermo E. Negro?n-Silva, Oscar R. Sua?rez-Castillo, and Jose? M. Va?squez-Pe?rez Inorg. Chem., 2017, 56, 2092?2099
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 of salt 1 with Cu2O and KI yields a second hybrid NHC/MIC proligand featuring a tetraiodocuprate anion [NHC(H+)-MIC(H+)][Cu2I4]2? (2). Through selective deprotonation and metalation, both salts 1 and 2 can generate either the chelate heterodicarbene complexes (3) with the rare [NHC(M)MIC]+[MX2]? general formula (M = PdII, RhI) or NHC-anchored/pendent triazolium species (4) [NHC(M)-MIC(H+)]. If the triazolium moiety of type 4 complexes is deprotonated with KHMDS in the presence of a second metal center, a series of heterobimetallic complexes of the type [NHC(M)-MIC(M?)] (5) are achieved. Interestingly, the reaction of salt 2 with KHMDS yields the bimetallic copper heterodicarbene (6) which can be a useful transfer reagent for the preparation of type 3 complexes. A variety of synthetic routes for the preparation of complexes 3?5 and their full characterization in solution and in the solid state will be discussed.