Gold(III) Alkyne Complexes: Bonding and Reaction Pathways
Rocchigiani, Luca, Fernandez-Cestau, Julio, Agonigi, Gabriele, Chambrier, Isabelle, Budzelaar, Peter and Bochmann, Manfred (2017) Gold(III) Alkyne Complexes: Bonding and Reaction Pathways. Angewandte Chemie International Edition, 56 (44). 13861–13865. ISSN 1433-7851
![]()
|
PDF (Accepted manuscript)
- Submitted Version
Available under License Creative Commons Attribution Non-commercial No Derivatives. Download (1MB) | Preview |
|
![]()
|
PDF (ACIE 2017, 56, 13861OA)
- Published Version
Available under License Creative Commons Attribution Non-commercial No Derivatives. Download (1MB) | Preview |
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: | 05 Feb 2021 01:32 |
URI: | https://ueaeprints.uea.ac.uk/id/eprint/64842 |
DOI: | 10.1002/anie.201708640 |
Actions (login required)
![]() |
View Item |