Gold(III) alkyne complexes: Bonding and reaction pathways

Rocchigiani, Luca ORCID: https://orcid.org/0000-0002-2679-8407, Fernandez-Cestau, Julio, Agonigi, Gabriele, Chambrier, Isabelle, Budzelaar, Peter and Bochmann, Manfred ORCID: https://orcid.org/0000-0001-7736-5428 (2017) Gold(III) alkyne complexes: Bonding and reaction pathways. Angewandte Chemie International Edition, 56 (44). 13861–13865. ISSN 1433-7851

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Abstract

The synthesis and characterization of hitherto hypothetical AuIII π-alkyne complexes is reported. Bonding and stability depend strongly on the trans effect and steric factors. Bonding characteristics shed light on the reasons for the very different stabilities between the classical alkyne complexes of PtII and their drastically more reactive AuIII congeners. Lack of back-bonding facilitates alkyne slippage, which is energetically less costly for gold than for platinum and explains the propensity of gold to facilitate C−C bond formation. Cycloaddition followed by aryl migration and reductive deprotonation is presented as a new reaction sequence in gold chemistry.

Item Type:	Article
Uncontrolled Keywords:	alkynes,density functional calculations,gold,homogeneous catalysis,reaction mechanisms
Faculty \ School:	Faculty of Science > School of Chemistry
Depositing User:	Pure Connector
Date Deposited:	13 Sep 2017 05:07
Last Modified:	21 Oct 2022 16:30
URI:	https://ueaeprints.uea.ac.uk/id/eprint/64842
DOI:	10.1002/anie.201708640

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