Gold(III) π‐Allyl Complexes

• Published in: Angewandte Chemie International Edition Vol. 59; no. 4; pp. 1511 - 1515
• Main Authors: Rodriguez, Jessica, Szalóki, György, Sosa Carrizo, E. Daiann, Saffon‐Merceron, Nathalie, Miqueu, Karinne, Bourissou, Didier
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 20.01.2020; Wiley Subscription Services, Inc; Wiley-VCH Verlag
• Edition: International ed. in English
• Subjects: Alkenes; Alkynes; allyl ligands; Aromatic compounds; Chemical Sciences; Chemistry; Chemistry, Multidisciplinary; Crystallography; Gold; gold(III) complexes; nucleophilic Addition; Organic chemistry; Organometallic compounds; Physical Sciences; Science & Technology; structure elucidation; π-complexes; GOLD-CATALYZED ALLYLATION; ACTIVATION; INSERTION; pi-complexes; nucleophilic Addition; gold(III) complexes; REACTIVITY; CHEMISTRY; GENERATION; structure elucidation; OXIDATIVE ADDITION; allyl ligands; π-complexes; allyl ligands gold(III) complexes nucleophilic Addition π-complexes structure elucidation
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201912314

Gold(III) π‐complexes have been authenticated recently with alkenes, alkynes, and arenes. The key importance of PdII π‐allyl complexes in organometallic chemistry (Tsuji–Trost reaction) prompted us to explore gold(III) π‐allyl complexes, which have remained elusive so far. The (P,C)AuIII(allyl) and (methallyl) complexes 3 and 3′ were readily prepared and isolated as thermally and air‐stable solids. Spectroscopic and crystallographic analyses combined with detailed DFT calculations support tight quasi‐symmetric η3‐coordination of the allyl moiety. The π‐allyl gold(III) complexes are activated towards nucleophilic additions, as substantiated with β‐diketo enolates. Go for gold: The π coordination of allyl moieties to (P,C) coordinated gold(III) has been authenticated and shown to promote nucleophilic addition. Spectroscopic and crystallographic analyses combined with detailed DFT calculations support tight quasi‐symmetric η3‐coordination of the allyl moiety.