Palladation of N3-alkylated 1,2,3-triazolium salts with Pd(OAc) 2 afforded a μ 2 -I 2 bridged bimetallic complex [Pd(trz)I 2 ] 2 and monometallic bis(carbene) complexes Pd(trz) 2 I 2 as a mixture of trans and cis isomers (trz = 1,2,3-triazol-5-ylidene). Addition of excess halide or modification of the palladation procedure from direct functionalization to a transmetalation sequence involving a silver intermediate allowed for chemoselective formation of the bis(carbene) complex, while subsequent anion metathesis with NaI produced the monometallic bis(carbene) complexes exclusively. Modification of the wingtip group had little influence on the metalation to palladium or rhodium(I) via transmetalation. According to NMR analysis using δ C and 1 J Rh-C , subtle but noticeable tunability of the metal electronic properties was identified. In addition, phenyl wingtip groups as N-substituents in the triazolylidene ligands were susceptible to cyclopalladation in the presence of NaOAc and are thus not chemically inert.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.