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Synthesis and tunability of abnormal 1,2,3-triazolylidene palladium and rhodium complexes

  • Poulain, Aurélie Department of Chemistry, University of Fribourg, Switzerland
  • Canseco-Gonzalez, Daniel School of Chemistry & Chemical Biology, University College Dublin, Ireland
  • Hynes-Roche, Rachel School of Chemistry & Chemical Biology, University College Dublin, Ireland
  • Müller-Bunz, Helge School of Chemistry & Chemical Biology, University College Dublin, Ireland
  • Schuster, Oliver Department of Chemistry, University of Fribourg, Switzerland
  • Stoeckli-Evans, Helen Institute of Physics, University of Neuchâtel, Switzerland
  • Neels, Antonia XRD Application Lab, CSEM, Rue Jaquet-Droz 1, CH-2002 Neuchâtel, Switzerland
  • Albrecht, Martin Department of Chemistry, University of Fribourg, Switzerland - School of Chemistry & Chemical Biology, University College Dublin, Ireland
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    18.01.2011
Published in:
  • Organometallics. - 2011, vol. 30, no. 5, p. 1021–1029
English 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 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 δC and ¹JRh−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.
Faculty
Faculté des sciences et de médecine
Department
Département de Chimie
Language
  • English
Classification
Chemistry
License
License undefined
Identifiers
Persistent URL
https://folia.unifr.ch/unifr/documents/301767
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