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High-coordinate gold(I) complexes with dithiocarboxylate ligands.

Christoph Kaub1, Timo Augenstein, Thomas O Bauer

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Ferrocene dithiocarboxylate ligands were used to synthesize novel gold(I) and copper(I) complexes, revealing flexible coordination modes and unusual coordination numbers for gold. These findings expand the coordination chemistry of coinage metals.

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Area of Science:

  • Organometallic Chemistry
  • Coordination Chemistry
  • Inorganic Chemistry

Background:

  • Ferrocene derivatives are versatile ligands in organometallic chemistry.
  • Gold(I) and copper(I) complexes are of interest due to their catalytic and medicinal applications.
  • Dithiocarboxylate ligands offer diverse coordination possibilities.

Purpose of the Study:

  • To synthesize and characterize novel gold(I) and copper(I) complexes using ferrocene dithiocarboxylate.
  • To investigate the coordination behavior and structural diversity of these complexes.
  • To explore the coordination flexibility of the ferrocene dithiocarboxylate ligand.

Main Methods:

  • Modified synthesis of piperidinium ferrocene dithiocarboxylate.
  • Reaction of the ferrocene dithiocarboxylate with gold(I) and copper(I) precursors in the presence of phosphine ligands.
  • Structural characterization of the resulting complexes using X-ray diffraction and (57)Fe-Mössbauer spectroscopy.

Main Results:

  • Successful synthesis of monomeric, dimeric, and polymeric gold(I) complexes with unusual three- and four-fold coordination.
  • Isolation of [(FcCSS)Au(PPh3)2], [(FcCSS)Au2(dppm)2], [(FcCSS)Au(dppf)]n, and [{(FcCSS)Au}2(dppp)] complexes.
  • Demonstration of the ferrocene dithiocarboxylate ligand's flexible coordination modes (monodentate, chelating, bridging) in gold complexes.
  • Synthesis of a copper(I) complex, [(FcCSS)Cu(PPh3)2].
  • (57)Fe-Mössbauer spectroscopy confirmed the diamagnetic nature of the ferrocene moieties in gold complexes.

Conclusions:

  • Ferrocene dithiocarboxylate is a versatile ligand for gold(I) and copper(I) chemistry.
  • The ligand enables the formation of complexes with diverse structures and coordination numbers.
  • This work expands the known coordination chemistry of coinage metals with ferrocene-based ligands.