Exploring Coordination Modes: Late Transition Metal Complexes with a Methylene-bridged Macrocyclic Tetra-NHC Ligand

Philipp J. Altmann, Daniel T. Weiss, Christian Jandl, Fritz E. Kühn

Research output: Contribution to journalArticlepeer-review

39 Scopus citations

Abstract

A tetranuclear silver(I) N-heterocyclic carbene (NHC) complex bearing a macrocyclic, exclusively methylene-bridged, tetracarbene ligand was synthesized and employed as transmetalation agent for the synthesis of nickel(II), palladium(II), platinum(II), and gold(I) derivatives. The transition metal complexes exhibit different coordination geometries, the coinage metals being bound in a linear fashion forming molecular box-type complexes, whereas the group 10 metals adapt an almost ideal square planar coordination geometry within the ligand's cavity, resulting in saddle-shaped complexes. Both the AgI and the AuI complexes show ligand-induced metal-metal contacts, causing photoluminescence in the blue region for the gold complex. Distinct metal-dependent differences of the coordination behavior between the group 10 transition metals were elucidated by low-temperature NMR spectroscopy and DFT calculations. Ag complex issue: A tetranuclear silver complex bearing an exclusively methylene-bridged, macrocyclic NHC ligand is synthesized and employed as transmetalation reagent for the synthesis of a series of d-block metal complexes. Their structural characteristics, photoluminescent properties, and ligand dynamics were investigated by X-ray crystallography, NMR spectroscopy, absorption and emission spectroscopy as well as DFT calculations.

Original languageEnglish
Pages (from-to)1597-1605
Number of pages9
JournalChemistry - An Asian Journal
Volume11
Issue number10
DOIs
StatePublished - 20 May 2016

Keywords

  • late transition metals
  • macrocyclic ligands
  • N-heterocyclic carbenes
  • photoluminescence
  • transmetalation

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