Gold(III) alkyne complexes: Bonding and reaction pathways

Luca Rocchigiani; Julio Fernandez-Cestau; Gabriele Agonigi; Isabelle Chambrier; Peter Budzelaar; Manfred Bochmann

doi:10.1002/anie.201708640

Gold(III) alkyne complexes: Bonding and reaction pathways

Luca Rocchigiani, Julio Fernandez-Cestau, Gabriele Agonigi, Isabelle Chambrier, Peter Budzelaar, Manfred Bochmann

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Abstract

The synthesis and characterization of hitherto hypothetical Au^III 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 Pt^II and their drastically more reactive Au^III 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.

Original language	English
Pages (from-to)	13861–13865
Number of pages	5
Journal	Angewandte Chemie-International Edition
Volume	56
Issue number	44
Early online date	2 Oct 2017
DOIs	https://doi.org/10.1002/anie.201708640
Publication status	Published - 23 Oct 2017

Keywords

alkynes
density functional calculations
gold
homogeneous catalysis
reaction mechanisms

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10.1002/anie.201708640Licence: CC BY-NC-ND

Accepted manuscriptAccepted author manuscript, 1.16 MBLicence: CC BY-NC-ND
ACIE 2017, 56, 13861OAFinal published version, 1.05 MBLicence: CC BY-NC-ND

Manfred Bochmann
- M.Bochmannuea.acuk
- School of Chemistry, Pharmacy and Pharmacology - Emeritus Professor
- Chemistry of Light and Energy - Member
- Chemistry of Materials and Catalysis - Member
Person: Honorary, Research Group Member

Cite this

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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.",

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T1 - Gold(III) alkyne complexes: Bonding and reaction pathways

AU - Rocchigiani, Luca

AU - Fernandez-Cestau, Julio

AU - Agonigi, Gabriele

AU - Chambrier, Isabelle

AU - Budzelaar, Peter

AU - Bochmann, Manfred

PY - 2017/10/23

Y1 - 2017/10/23

N2 - 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.

AB - 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.

KW - alkynes

KW - density functional calculations

KW - gold

KW - homogeneous catalysis

KW - reaction mechanisms

U2 - 10.1002/anie.201708640

DO - 10.1002/anie.201708640

M3 - Article

VL - 56

SP - 13861

EP - 13865

JO - Angewandte Chemie-International Edition

JF - Angewandte Chemie-International Edition

SN - 1433-7851

IS - 44

ER -

Gold(III) alkyne complexes: Bonding and reaction pathways

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Manfred Bochmann

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