Poulain, Aurélie Canseco-Gonzalez, Daniel Hynes-Roche, Rachel Müller-Bunz, Helge Schuster, Oliver Stoeckli-Evans, Helen Neels, Antonia Albrecht, Martin 2011-01-18 Palladation of N3-alkylated 1,2,3-triazolium salts with Pd(OAc)₂ afforded a μ²−I₂ bridged bimetallic complex [Pd(trz)I₂]₂ and monometallic bis(carbene) complexes Pd(trz)₂I₂ as a mixture of <i>trans</i> and <i>cis</i> 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<i>J</i>_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. application/pdf https://folia.unifr.ch/global/documents/301767 https://folia.unifr.ch/documents/301767/files/pou_sta.pdf https://folia.unifr.ch/documents/301767/files/pou_sta_sm.pdf https://folia.unifr.ch/documents/301767/files/pou_sta_sm_cif.txt eng info:eu-repo/semantics/altIdentifier/doi/10.1021/om101076u info:eu-repo/semantics/openAccess License undefined Organometallics. - 2011, vol. 30, no. 5, p. 1021–1029 info:eu-repo/classification/udc/54 Synthesis and tunability of abnormal 1,2,3-triazolylidene palladium and rhodium complexes http://purl.org/coar/resource_type/c_6501