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Analysis of institutional authors

Fernández, EstefaníaAuthorFernandez, EAuthorCabrero-Antonino, MAuthorGavara, RAuthorCorma, ACorresponding Author

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October 30, 2024
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Article

Base-Controlled Heck, Suzuki, and Sonogashira Reactions Catalyzed by Ligand-Free Platinum or Palladium Single Atom and Sub-Nanometer Clusters

Publicated to: Journal Of The American Chemical Society. 141 (5): 1928-1940 - 2019-02-06 141(5), DOI: 10.1021/jacs.8b07884

Authors:

Fernández, E; Rivero-Crespo, MA; Domínguez, I; Rubio-Marqués, P; Oliver-Meseguer, J; Liu, LC; Cabrero-Antonino, M; Gavara, R; Hernández-Garrido, JC; Boronat, M; Leyva-Pérez, A; Corma, A
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Affiliations

CSIC, Inst Agroquim & Tecnol Alimentos, Packaging Lab, Ave Agustin Escardino 7 - Author
Univ Cadiz, Dept Ciencia Mat & Ingn Met & Quim Inorgan, Campus Rio San Pedro - Author
Univ Politecn Valencia, Inst Tecnol Quim, CSIC, Avda Naranjos S-N - Author
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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.
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Keywords

Addition reactionsAdsorptionAminesArticleAryl iodidesAtomsBondC-cCatalysisCatalystCatalystsChelationChemical analysisChemical reactionChlorine compoundsComputational studiesCross coupling reactionCross coupling reactionsDensity functional theoryEffective core potentialsEnergy dispersive x ray spectroscopyFinding saddle-pointsHeck reactionInductively coupled plasma mass spectrometryInfrared spectroscopyLigandsLight scatteringLow temperatureMechanismMetalMetal halidesMolecular calculationsOrganic synthesisOrthogonal reactivitiesOxidative additionOxidative additionsPalladiumPhoton correlation spectroscopyPlatinumReactivity controlReductive eliminationSonogashira reactionsStereospecificityStoichiometrySuzuki reactionSynthesisThermodynamicsTransmission electron microscopyZeta potential

Quality index

Bibliometric impact. Analysis of the contribution and dissemination channel

The work has been published in the journal Journal Of The American Chemical Society due to its progression and the good impact it has achieved in recent years, according to the agency WoS (JCR), it has become a reference in its field. In the year of publication of the work, 2019, it was in position 13/177, thus managing to position itself as a Q1 (Primer Cuartil), in the category Chemistry, Multidisciplinary. Notably, the journal is positioned above the 90th percentile.

From a relative perspective, and based on the normalized impact indicator calculated from World Citations provided by WoS (ESI, Clarivate), it yields a value for the citation normalization relative to the expected citation rate of: 3.28. This indicates that, compared to works in the same discipline and in the same year of publication, it ranks as a work cited above average. (source consulted: ESI Nov 13, 2025)

This information is reinforced by other indicators of the same type, which, although dynamic over time and dependent on the set of average global citations at the time of their calculation, consistently position the work at some point among the top 50% most cited in its field:

  • Weighted Average of Normalized Impact by the Scopus agency: 4.41 (source consulted: FECYT Mar 2025)

Specifically, and according to different indexing agencies, this work has accumulated citations as of 2026-02-11, the following number of citations:

  • WoS: 120
  • Scopus: 123
  • Europe PMC: 17
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Impact and social visibility

From the perspective of influence or social adoption, and based on metrics associated with mentions and interactions provided by agencies specializing in calculating the so-called "Alternative or Social Metrics," we can highlight as of 2026-02-11:

  • The use, from an academic perspective evidenced by the Altmetric agency indicator referring to aggregations made by the personal bibliographic manager Mendeley, gives us a total of: 109.
  • The use of this contribution in bookmarks, code forks, additions to favorite lists for recurrent reading, as well as general views, indicates that someone is using the publication as a basis for their current work. This may be a notable indicator of future more formal and academic citations. This claim is supported by the result of the "Capture" indicator, which yields a total of: 109 (PlumX).

With a more dissemination-oriented intent and targeting more general audiences, we can observe other more global scores such as:

  • The Total Score from Altmetric: 5.
  • The number of mentions on the social network X (formerly Twitter): 9 (Altmetric).

It is essential to present evidence supporting full alignment with institutional principles and guidelines on Open Science and the Conservation and Dissemination of Intellectual Heritage. A clear example of this is:

  • The work has been submitted to a journal whose editorial policy allows open Open Access publication.
  • Assignment of a Handle/URN as an identifier within the deposit in the Institutional Repository: http://hdl.handle.net/10251/202499
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Leadership analysis of institutional authors

There is a significant leadership presence as some of the institution’s authors appear as the first or last signer, detailed as follows: First Author (FERNÁNDEZ DE VELASCO SANZ, ESTIBALIZ) and Last Author (Corma Canós, Avelino).

the authors responsible for correspondence tasks have been Boronat, M, Leyva-Pérez, A and Corma Canós, Avelino.

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Awards linked to the item

This work was supported by the MINECO (Spain) (projects CTQ2017-86735-P and Excellence Unit "Severo Ochoa" SEV-2016-0683). E.F.V. and M.M. thank MINECO for their fellowship SVP-2013-068146 and a predoctoral contract. We thank Jose M. Coll-Marques for performing the micro fluorescence measure-ments. Red Espanola de Supercomputacion (RES) and Centre de Cacul de la Universitat de Valencia are gratefully acknowledged for computational resources.
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