Gem-diaurated gold(III) complexes

• Verfasst von: Wunsch, Jonas [VerfasserIn]
• Verfasst von: Eberle, Lukas [VerfasserIn]
• Verfasst von: Mullen, Joseph P. [VerfasserIn]
• Verfasst von: Rominger, Frank [VerfasserIn]
• Verfasst von: Rudolph, Matthias [VerfasserIn]
• Verfasst von: Hashmi, A. Stephen K. [VerfasserIn]
• Titel: Gem-diaurated gold(III) complexes
• Titelzusatz: synthesis, structure, aurophilic interaction, and catalytic activity
• Verf.angabe: Jonas F. Wunsch, Lukas Eberle, Joseph P. Mullen, Frank Rominger, Matthias Rudolph and A. Stephen K. Hashmi
• E-Jahr: 2022
• Jahr: February 18, 2022
• Umfang: 8 S.
• Fussnoten: Gesehen am 05.07.2022
• Titel Quelle: Enthalten in: Inorganic chemistry
• Ort Quelle: Washington, DC : American Chemical Society, 1962
• Jahr Quelle: 2022
• Band/Heft Quelle: 61(2022), 8, Seite 3508-3515
• ISSN Quelle: 1520-510X
• DOI: doi:10.1021/acs.inorgchem.1c03479
• Datenträger: Online-Ressource
• Sprache: eng
• K10plus-PPN: 1809190584

Abstract

We present a protocol to synthesize air stable gem-diaurated gold(III) compounds from 1,3-diketones in a single cycloauration step with tetrachloroauric acid. So far related species were only accessible from phosphonium bis(ylide) ligands which hold the two gold atoms in close proximity. Lacking such a constraint, our compounds show the longest Au-Au distances of all gem-diaurated carbons, ranging from 3.26 to 3.32 Å. Modeling based on results of CCSD(T) calculations shows no stabilization by aurophilic interactions for our gold(III) systems, compared to 9.1 kcal/mol for gold(I) gem-diauration. This demonstrates no aurophilic interactions are needed for the isolation of air stable gem-diaurated gold(III) complexes. We show the new gem-diaurated gold(III) compounds are active in the gold-catalyzed phenol synthesis and highly active in the cycloisomerization of an N-propargylcarboxamide; here, we obtained the so far highest known TON of over 2500 per gold atom with respect to the oxazole formation.