A merged copper(I/II) cluster isolated from Glaser coupling.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 31649254.
- Also identified by DOI 10.1038/s41467-019-12889-w and PMC identifier 6813345.
- Licence recorded as CC BY.
- The licence permits redistribution, so the abstract is shown in full and the full text is available from the publisher.
Abstract
Ubiquitous copper-oxygen species are pivotal in enabling multifarious oxidation reactions in biological and chemical transformations. We herein construct a macrocycle-protected mixed-valence cluster [(<sup>t</sup>BuC≡CCu<sup>I</sup><sub>3</sub>)-(μ<sub>2</sub>-OH)-Cu<sup>II</sup>] by merging a copper acetylide cluster with a copper-oxygen moiety formed in Glaser coupling. This merged Cu(I/II) cluster shows remarkably strong oxidation capacity, whose reduction potential is among the most positive for Cu(II) and even comparable with some Cu(III) species. Consequently, the cluster exhibits high hydrogen atom transfer (HAT) reactivity with inert hydrocarbons. In contrast, the degraded [Cu<sup>II</sup>-(μ<sub>2</sub>-OH)-Cu<sup>II</sup>] embedded in a small macrocyclic homologue shows no HAT reactivity. Theoretical calculations indicate that the strong oxidation ability of Cu(II) in [(<sup>t</sup>BuC≡CCu<sup>I</sup><sub>3</sub>)-(μ<sub>2</sub>-OH)-Cu<sup>II</sup>] is mainly ascribed to the uneven charge distribution of Cu(I) ions in the <sup>t</sup>BuC≡CCu<sup>I</sup><sub>3</sub> unit because of significant [d<sub>Cu(I)</sub> → π*<sub>(C≡C)</sub>] back donation. The present study on in situ formed metal clusters opens a broad prospect for mechanistic studies of Cu-based catalytic reactions.