Detaching thiolates from copper and gold clusters: Which bonds to break?

Martin Konôpka, Roger Rousseau, Ivan Štich, Dominik Marx

Research output: Contribution to journalArticlepeer-review

84 Citations (Scopus)


The interaction of alkanethiolates with small coinage metal clusters of copper and gold was studied based on density functional theory with a focus on the metal-thiolate junction. Calculation of fragmentation energies indicate that for Cun-thiolate (n = 1,3,5,7, and 9) there is a progressive lowering in energy for the fragmentation of the S-C bond in the thiolate from a value of 2.9 eV for n = 1 to 1.4 eV for n = 9. The detailed electronic origins of this specific weakening are attributed to a polarization of electron density in the S-C bond as induced by bonding with the Cun cluster. For the gold analogues, this effect is not observed and fragmentation at the S-C bond experiences only a slight 10% destabilization as n increases from 3 to 9. The relativistic origin of this difference between Cu and Au is discussed, and an analysis of bonding considerations is presented.

Original languageEnglish
Pages (from-to)12103-12111
Number of pages9
JournalJournal of the American Chemical Society
Issue number38
Publication statusPublished - Sep 29 2004

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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