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. 2025 Jun 4;44(12):1241-1245.
doi: 10.1021/acs.organomet.5c00081. eCollection 2025 Jun 23.

Flash Communication: Challenging Computational Description of Gold(I)/Gold(III) Catalytic Cycles

Isabel Arranz  1   2 , Feliu Maseras  1   2 , Antonio M Echavarren  1   2
Affiliations

Flash Communication: Challenging Computational Description of Gold(I)/Gold(III) Catalytic Cycles

Isabel Arranz et al. Organometallics. .

Abstract

We have investigated the mechanism of cross-coupling reactions catalyzed by gold-(I) complexes without the assistance of chelating ligands. Following pioneering studies by Kochi, gold-(I) complexes with simple alkyl phosphines as ligands are considered. The reaction between cinnamyl bromide and PhSnMe3 is experimentally shown to take place in the presence of a [Me3PAuCl] complex. However, our attempt to characterize computationally, using density functional theory (DFT), a mechanism following a plausible gold-(I)/gold-(III) catalytic cycle unearths an unexpectedly complex situation, showing a large range of energy values computed with different functionals.

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Figures

1
1. a) Oxidative Addition of MeI to Gold­(I) and Reductive Elimination. , b) Gold­(I)-Catalyzed Coupling of Allyl Bromide with PhB­(OH)2
2
2. Simplified Cycle for Gold­(I)-Catalyzed Cross-Coupling of Cinnamyl Bromide with PhSnMe3
3
3. Mechanistic Pathway Submitted to DFT Benchmarking
See this image and copyright information in PMC

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