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
    info

    Universidad de La Rioja

    Logroño, España

    ROR https://ror.org/0553yr311

Journal:
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

Abstract

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).