We critically review recent experimental and theoretical investigations into some key aspects of the chemistry of gold(I) complexes of the type [L–Au–S]+X– (L = NHC carbenes and phosphanes, S = alkenes and alkynes, and X– = weakly coordinating counterion). These systems are important intermediates formed during gold-catalyzed nucleophilic additions to an unsaturated substrate, and their specific activity is largely governed by two fundamental factors: the nature of the gold–substrate bond and the role of the ion-pair structure in solution. Both are crucially influenced by the nature and properties of the auxiliary ligand L, and on this interplay we focus our discussion. The relative anion–cation orientation, investigated by NOE NMR spectroscopy and DFT calculations, shows that the exact position of the counterion is determined by the natures of the ancillary ligand and substrate: the counterion is located near the substrate in the phosphane complexes, while for the NHC complexes the preferred position of the counterion is near the ligand. This tunable interionic structure opens the way to greater control over the properties and activity of these catalysts. The bond between AuI and the unsaturated substrate is investigated using an original and powerful theoretical method of analysis. Our approach permits a rigorous definition and assessment of the charge-displacement (CD) components at the heart of the Dewar–Chatt–Duncanson model: substrate-to-metal (σ donation) and metal-to-substrate (π back-donation) and how these change with different ligands. The results consistently reveal that π back-donation is a large and crucially important component of the AuI–substrate bond in all systems: π back-donation penetrates the external side of coordinated alkynes, where nucleophile attack is directed, thus partially mitigating the electron depletion caused by σ donation.

Ligand Effects on Bonding and Ion Pairing in Cationic Gold(I) Catalysts Bearing Unsaturated Hydrocarbons

ZUCCACCIA, DANIELE;BELPASSI, LEONARDO;MACCHIONI, Alceo;TARANTELLI, Francesco
2013

Abstract

We critically review recent experimental and theoretical investigations into some key aspects of the chemistry of gold(I) complexes of the type [L–Au–S]+X– (L = NHC carbenes and phosphanes, S = alkenes and alkynes, and X– = weakly coordinating counterion). These systems are important intermediates formed during gold-catalyzed nucleophilic additions to an unsaturated substrate, and their specific activity is largely governed by two fundamental factors: the nature of the gold–substrate bond and the role of the ion-pair structure in solution. Both are crucially influenced by the nature and properties of the auxiliary ligand L, and on this interplay we focus our discussion. The relative anion–cation orientation, investigated by NOE NMR spectroscopy and DFT calculations, shows that the exact position of the counterion is determined by the natures of the ancillary ligand and substrate: the counterion is located near the substrate in the phosphane complexes, while for the NHC complexes the preferred position of the counterion is near the ligand. This tunable interionic structure opens the way to greater control over the properties and activity of these catalysts. The bond between AuI and the unsaturated substrate is investigated using an original and powerful theoretical method of analysis. Our approach permits a rigorous definition and assessment of the charge-displacement (CD) components at the heart of the Dewar–Chatt–Duncanson model: substrate-to-metal (σ donation) and metal-to-substrate (π back-donation) and how these change with different ligands. The results consistently reveal that π back-donation is a large and crucially important component of the AuI–substrate bond in all systems: π back-donation penetrates the external side of coordinated alkynes, where nucleophile attack is directed, thus partially mitigating the electron depletion caused by σ donation.
2013
File in questo prodotto:
Non ci sono file associati a questo prodotto.

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11391/1137873
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 68
  • ???jsp.display-item.citation.isi??? 68
social impact