Disproportionation of Gold(II) Complexes. A Density Functional Study of Ligand and Solvent Effects

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This article discusses disproportionation of gold(II) as an atomic ion as well as with chloride and neutral ligands.

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7 p.

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Barakat, Khaldoon A.; Cundari, Thomas R., 1964-; Rabaâ, Hassan & Omary, Mohammad A. July 13, 2006.

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This article discusses disproportionation of gold(II) as an atomic ion as well as with chloride and neutral ligands.

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7 p.

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Reprinted with permission from the Journal of Physical Chemistry B. Copyright 2006 American Chemical Society.

Abstract: A computational study of gold(II) disproportionation is presented for the atomic ion as well as complexes with chloride and neutral ligands. The Au²⁺ atomic ion is stable to disproportionation, but the barrier is more than halved to 119 kcal/mol in an aqueous environment vs 283 kcal/mol in the gas phase. For dissociative disproportionation of chloride complexes, the loss of chlorine, either as an atom (∆Gaq = +20 kcal/mol) or as an anion (∆Gaq = +15 kcal/mol) represents the largest calculated barrier. The calculated transition state for associative disproportionation is only 9 kcal/mol above separated Auᴵᴵ complex, a nonpolar solvent is preferred. With the exception of [Au(CO₃]²⁺, disproportionation of AuᴵᴵL₃ complexes to AuᴵL and AuᴵᴵᴵL₃ is exergonic in solution phase for the ligands investigated. The driving force is provided by the very favorable solvation free energy of the trivalent gold complex. The solvation free energy contribution to the reaction (∆Gsolv) is very large for small and polar ligands such as ammonia and water. Furthermore, calculations imply that choosing ligands that would yield neutral species upon disproportionation may provide an effective route to thwart this decomposition pathway for Auᴵᴵ complexes. Likewise, bulkier ligands that yield larger, more weakly solvated complex ions would appear to be desirable.

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  • Journal of Physical Chemistry B, 2006, Washington D.C.: American Chemical Society, pp. 14645-14651

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  • Publication Title: Journal of Physical Chemistry B
  • Volume: 110
  • Page Start: 14645
  • Page End: 14651
  • Pages: 7
  • Peer Reviewed: Yes

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  • July 13, 2006

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  • March 9, 2012, 2:17 p.m.

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  • Jan. 9, 2015, 5:13 p.m.

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Barakat, Khaldoon A.; Cundari, Thomas R., 1964-; Rabaâ, Hassan & Omary, Mohammad A. Disproportionation of Gold(II) Complexes. A Density Functional Study of Ligand and Solvent Effects, article, July 13, 2006; [Washington, D.C.]. (digital.library.unt.edu/ark:/67531/metadc77172/: accessed April 29, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT College of Arts and Sciences.