The key role of Au-substrate interactions in catalytic gold subnanoclusters

  1. Cordón, J. 1
  2. Jiménez-Osés, G. 1
  3. López-De-Luzuriaga, J.M. 1
  4. Monge, M. 1
  1. 1 Universidad de La Rioja

    Universidad de La Rioja

    Logroño, España


Nature Communications

ISSN: 2041-1723

Year of publication: 2017

Volume: 8

Issue: 1

Type: Article

DOI: 10.1038/s41467-017-01675-1 SCOPUS: 2-s2.0-85034751587 WoS: WOS:000416039200009 GOOGLE SCHOLAR
Institutional repository: lock_openOpen access editor


The development of gold catalysis has allowed significant levels of activity and complexity in organic synthesis. Recently, the use of very active small gold subnanoclusters (Au n, n < 10) has been reported. The stabilization of such nanocatalysts to prevent self-aggregation represents a true challenge that has been partially remediated, for instance, by their immobilization in polymer matrices. Here, we describe the transient stabilization of very small gold subnanoclusters (Au n, n < 5) by alkyl chains or aromatic groups appended to the reactive π bond of simple alkynes. The superior performance toward Brønsted acid-free hydration of medium to long aliphatic alkynes (1-hexyne and 1-docecyne) and benzylacetylene with respect to phenylacetylene is demonstrated experimentally and investigated computationally. A cooperative network of dispersive Au···C-H and/or Au···π interactions, supported by quantum mechanical calculations and time-resolved luminescence experiments, is proposed to be at the origin of this stabilization. © 2017 The Author(s).