Gem-diaurated gold(III) complexes: synthesis, structure, aurophilic interaction, and catalytic activity
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 suc...
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| Hauptverfasser: | , , , , , |
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| Dokumenttyp: | Article (Journal) |
| Sprache: | Englisch |
| Veröffentlicht: |
February 18, 2022
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| In: |
Inorganic chemistry
Year: 2022, Jahrgang: 61, Heft: 8, Pages: 3508-3515 |
| ISSN: | 1520-510X |
| DOI: | 10.1021/acs.inorgchem.1c03479 |
| Online-Zugang: | Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1021/acs.inorgchem.1c03479
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| Verfasserangaben: | Jonas F. Wunsch, Lukas Eberle, Joseph P. Mullen, Frank Rominger, Matthias Rudolph and A. Stephen K. Hashmi |
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| 520 | |a 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. | ||
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