Base-Controlled Heck, Suzuki, and Sonogashira Reactions Catalyzed by Ligand-Free Platinum or Palladium Single Atom and Sub-Nanometer Clusters. Fernández, E.; Rivero-Crespo, M.; Domínguez, I.; Rubio-Marqués, P.; Oliver-Meseguer, J.; Liu, L.; Cabrero-Antonino, M.; Gavara, R.; Hernández-Garrido, J.; Boronat, M.; Leyva-Pérez, A.; and Corma, A. Journal of the American Chemical Society, 141(5):1928-1940, 2019. cited By 24
Base-Controlled Heck, Suzuki, and Sonogashira Reactions Catalyzed by Ligand-Free Platinum or Palladium Single Atom and Sub-Nanometer Clusters [link]Paper  doi  abstract   bibtex   
The assumption that oxidative addition is the key step during the cross-coupling reaction of aryl halides has led to the development of a plethora of increasingly complex metal catalysts, thereby obviating in many cases the exact influence of the base, which is a simple, inexpensive, and necessary reagent for this paramount transformation. Here, a combined experimental and computational study shows that the oxidative addition is not the single kinetically relevant step in different cross-coupling reactions catalyzed by sub-nanometer Pt or Pd species, since the reactivity control is shifted toward subtle changes in the base. The exposed metal atoms in the cluster cooperate to enable an extremely easy oxidative addition of the aryl halide, even chlorides, and allow the base to bifurcate the coupling. With sub-nanometer Pd species, amines drive to the Heck reaction, carbonate drives to the Sonogahira reaction, and phosphate drives to the Suzuki reaction, while for Pt clusters and single atoms, good conversion is only achieved using acetate as a base. This base-controlled orthogonal reactivity with ligand-free catalysts opens new avenues in the design of cross-coupling reactions in organic synthesis. © Copyright 2019 American Chemical Society.
@ARTICLE{Fernandez20191928,
author={Fernández, E. and Rivero-Crespo, M.A. and Domínguez, I. and Rubio-Marqués, P. and Oliver-Meseguer, J. and Liu, L. and Cabrero-Antonino, M. and Gavara, R. and Hernández-Garrido, J.C. and Boronat, M. and Leyva-Pérez, A. and Corma, A.},
title={Base-Controlled Heck, Suzuki, and Sonogashira Reactions Catalyzed by Ligand-Free Platinum or Palladium Single Atom and Sub-Nanometer Clusters},
journal={Journal of the American Chemical Society},
year={2019},
volume={141},
number={5},
pages={1928-1940},
doi={10.1021/jacs.8b07884},
note={cited By 24},
url={https://www.scopus.com/inward/record.uri?eid=2-s2.0-85061138227&doi=10.1021%2fjacs.8b07884&partnerID=40&md5=c6ab90699571e64604b6748909eaaf31},
abstract={The assumption that oxidative addition is the key step during the cross-coupling reaction of aryl halides has led to the development of a plethora of increasingly complex metal catalysts, thereby obviating in many cases the exact influence of the base, which is a simple, inexpensive, and necessary reagent for this paramount transformation. Here, a combined experimental and computational study shows that the oxidative addition is not the single kinetically relevant step in different cross-coupling reactions catalyzed by sub-nanometer Pt or Pd species, since the reactivity control is shifted toward subtle changes in the base. The exposed metal atoms in the cluster cooperate to enable an extremely easy oxidative addition of the aryl halide, even chlorides, and allow the base to bifurcate the coupling. With sub-nanometer Pd species, amines drive to the Heck reaction, carbonate drives to the Sonogahira reaction, and phosphate drives to the Suzuki reaction, while for Pt clusters and single atoms, good conversion is only achieved using acetate as a base. This base-controlled orthogonal reactivity with ligand-free catalysts opens new avenues in the design of cross-coupling reactions in organic synthesis. © Copyright 2019 American Chemical Society.},
keywords={Addition reactions;  Amines;  Atoms;  Catalysis;  Catalysts;  Chelation;  Chlorine compounds;  Ligands;  Metal halides;  Platinum, Computational studies;  Cross coupling reactions;  Organic synthesis;  Orthogonal reactivities;  Oxidative additions;  Reactivity control;  Sonogashira reactions;  Suzuki reaction, Palladium, palladium;  platinum, adsorption;  Article;  catalyst;  chemical analysis;  chemical reaction;  cross coupling reaction;  density functional theory;  energy dispersive X ray spectroscopy;  Heck reaction;  inductively coupled plasma mass spectrometry;  infrared spectroscopy;  light scattering;  low temperature;  photon correlation spectroscopy;  stereospecificity;  stoichiometry;  Suzuki reaction;  synthesis;  thermodynamics;  transmission electron microscopy;  zeta potential},
document_type={Article},
source={Scopus},
}
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