Chelation enforcing a dual gold configuration in the catalytic hydroxyphenoxylation of alkynes. (6th July 2021)

• Record Type: Journal Article
• Authors: Escayola, Sílvia; Poater, Jordi; Ramos, Miguel; Luque‐Urrutia, Jesús Antonio; Duran, Josep; Simon, Sílvia; Solà, Miquel; Cavallo, Luigi; Nolan, Steven P.; Poater, Albert
• Is Part Of: Applied organometallic chemistry. Volume 35:Number 10(2021)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2021-07-06
• Subjects: hydrophenoxylation -- DFT -- energy decomposition analysis -- gold -- C–O coupling; Organometallic chemistry -- Periodicals; Organometallic compounds -- Periodicals; 547.05
• DOI: 10.1002/aoc.6362
• Languages: English
• ISSNs: 0268-2605

Abstract

Abstract: The functionalization of alkynes by Au (N‐heterocyclic carbene, NHC) complexes via the hydrophenoxylation reaction is a paradigm for the discussion between mono and dual metal catalysis. With the aim of mimicking the framework containing two gold units, achieved with molecular boxes, two NHC ligands were joined here with a chelated chain and this motif was examined in the hydrophenoxylation/hydroalkoxylation reactions through DFT calculations. This synthetic motif transforms the standard hydrophenoxylation intermolecular reaction from an inter‐ into an intra‐molecular nucleophilic attack, when forming the C–O bond. Various chain lengths were tested with regard to the coordination of the alkyne to the cationic NHC‐gold(I) center. Abstract : The functionalization of alkynes by Au (N‐heterocyclic carbene, NHC) complexes via thehydrophenoxylation reaction is a paradigm for the discussion between mono anddual metal catalysis. Predictive catalysis by density functional theory (DFT)calculations has provided here diaurated chelated systems with the capacity tocarry out the hydrophenoxylation of alkynes, forcing the dual metal catalysis.By means of an energydecomposition analysis (EDA), we have observed remarkableorbital attractive interaction particularly favored for the chain of sevenmethylene units.