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Verfasst von:Yang, Yangyang [VerfasserIn]   i
 Eberle, Lukas [VerfasserIn]   i
 Mulks, Florian [VerfasserIn]   i
 Wunsch, Jonas [VerfasserIn]   i
 Zimmer, Marc [VerfasserIn]   i
 Rominger, Frank [VerfasserIn]   i
 Rudolph, Matthias [VerfasserIn]   i
 Hashmi, A. Stephen K. [VerfasserIn]   i
Titel:Trans influence of ligands on the oxidation of Gold(I) complexes
Verf.angabe:Yangyang Yang, Lukas Eberle, Florian F. Mulks, Jonas F. Wunsch, Marc Zimmer, Frank Rominger, Matthias Rudolph, and A. Stephen K. Hashmi
E-Jahr:2019
Jahr:September 26, 2019
Umfang:7 S.
Fussnoten:Gesehen am 06.11.2019
Titel Quelle:Enthalten in: American Chemical SocietyJournal of the American Chemical Society
Ort Quelle:Washington, DC : American Chemical Society, 1879
Jahr Quelle:2019
Band/Heft Quelle:141(2019), 43, Seite 17414-17420
ISSN Quelle:1520-5126
Abstract:Gold(I) complexes are considered active species toward oxidative addition; current understanding indicates a different mechanism in contrast to other late transition metals, but a rational understanding of the reactivity profile is lacking. Herein, we propose that the accessibility of the gold(I) center to tri- or tetra-coordination is critical in the oxidative process involving a tri- or tetra-coordinate gold(I) with the oxidizing reagent as one of the ligands as an intermediate. A computational study of the geometry of (Phen)R3PAu(I)NTf2 complexes shows that the accessibility of such tricoordinate species shows a good correlation with the “trans influence” of phosphine ligands: the weak σ-donating phosphine ligands promote tricoordination of gold(I) complexes. The oxidative addition to the asymmetric tricoordinate (Phen)R3PAu(I)NTf2 complexes with alkynyl hypervalent iodine reagents was built. The kinetic profile of the oxidative addition exhibits a good relationship to the Hammett substituent parameter (ρ = 3.75, R2 = 0.934), in which the gold(I) complexes bearing less σ-donating phosphine ligands increase the rate of oxidative addition. The positive ρ indicates a high sensitivity of the oxidative addition to the trans influence. The reactivity profile of oxidative addition to a linear bis(pyridine)gold(I) complex further supports that the oxidative addition to gold(I) complexes is promoted by ligands with small trans influence.
DOI:doi:10.1021/jacs.9b09363
URL:Bitte beachten Sie: Dies ist ein Bibliographieeintrag. Ein Volltextzugriff für Mitglieder der Universität besteht hier nur, falls für die entsprechende Zeitschrift/den entsprechenden Sammelband ein Abonnement besteht oder es sich um einen OpenAccess-Titel handelt.

Volltext: https://doi.org/10.1021/jacs.9b09363
 Verlag: https://pubs.acs.org/doi/10.1021/jacs.9b09363
 DOI: https://doi.org/10.1021/jacs.9b09363
Datenträger:Online-Ressource
Sprache:eng
K10plus-PPN:1681143011
Verknüpfungen:→ Zeitschrift

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