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.

https://www.nature.com/articles/s41467-017-01675-1