In this work, the mechanism of the insertion reaction of 3-hexyne into Cu−Al and Au−Al bonds in M−aluminyl (M = Cu, Au) complexes is computationally elucidated. The mechanism is found to be radical-like, with the Cu−Al and Au−Al bonds acting as nucleophiles toward the alkyne, and predicts a less efficient reactivity for the gold−aluminyl complex. The proposed mechanism well rationalizes the kinetic (or thermodynamic) control on the formation of the syn (or anti) insertion product into the Cu−Al bond (i.e., dimetallated alkene) which has been recently reported. A comparative analysis of the electronic structure reveals that the reduced reactivity at the gold site-usually showing higher efficiency than copper as a “standard” electrophile in alkyne activation-arises from a common feature, i.e., the highly stable 6s Au orbital. The relativistic lowering of the 6s orbital, making it more suitable for accepting electron density and thus enhancing the electrophilicity of gold complexes, in the gold−aluminyl system is responsible for a less nucleophilic Au−Al bond and, consequently, a less efficient alkyne insertion. These findings demonstrate that the unconventional electronic structure and the electron-sharing nature of the M−Al bond induce a paradigm shift in the properties of coinage metal complexes. In particular, the peculiar radical-like reactivity, previously shown also with carbon dioxide, suggests that these complexes might efficiently insert/activate other small molecules, opening new and unexplored paths for their reactivity.

Mechanistic study of alkyne insertion into Cu−Al and Au−Al bonds: a paradigm shift for coinage metal chemistry

Diego Sorbelli
;
Leonardo Belpassi
;
Paola Belanzoni
2022

Abstract

In this work, the mechanism of the insertion reaction of 3-hexyne into Cu−Al and Au−Al bonds in M−aluminyl (M = Cu, Au) complexes is computationally elucidated. The mechanism is found to be radical-like, with the Cu−Al and Au−Al bonds acting as nucleophiles toward the alkyne, and predicts a less efficient reactivity for the gold−aluminyl complex. The proposed mechanism well rationalizes the kinetic (or thermodynamic) control on the formation of the syn (or anti) insertion product into the Cu−Al bond (i.e., dimetallated alkene) which has been recently reported. A comparative analysis of the electronic structure reveals that the reduced reactivity at the gold site-usually showing higher efficiency than copper as a “standard” electrophile in alkyne activation-arises from a common feature, i.e., the highly stable 6s Au orbital. The relativistic lowering of the 6s orbital, making it more suitable for accepting electron density and thus enhancing the electrophilicity of gold complexes, in the gold−aluminyl system is responsible for a less nucleophilic Au−Al bond and, consequently, a less efficient alkyne insertion. These findings demonstrate that the unconventional electronic structure and the electron-sharing nature of the M−Al bond induce a paradigm shift in the properties of coinage metal complexes. In particular, the peculiar radical-like reactivity, previously shown also with carbon dioxide, suggests that these complexes might efficiently insert/activate other small molecules, opening new and unexplored paths for their reactivity.
2022
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/11391/1538213
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 4
  • ???jsp.display-item.citation.isi??? ND
social impact