Tetracopper σ‐Bound μ‐Acetylide and ‐Diyne Units Stabilized by a Naphthyridine‐based Dinucleating Ligand

Author:

Ríos Pablo12ORCID,See Matthew S.23ORCID,Handford Rex C.2ORCID,Cooper Jason K.3ORCID,Don Tilley T.23ORCID

Affiliation:

1. Instituto de Investigaciones Químicas (IIQ) Departamento de Química Inorgánica Centro de Innovación en Química Avanzada (ORFEO-CINQA) CSIC and Universidad de Sevilla 41092 Sevilla Spain

2. Department of Chemistry University of California Berkeley USA

3. Chemical Sciences Division Lawrence Berkeley National Laboratory Berkeley CA 94720 USA

Abstract

AbstractReactions of a dicopper(I) tert‐butoxide complex with alkynes possessing boryl or silyl capping groups resulted in formation of unprecedented tetracopper(I) μ‐acetylide/diyne complexes that were characterized by NMR and UV/Vis spectroscopy, mass spectrometry and single‐crystal X‐ray diffraction. These compounds possess an unusual μ4η1:η1:η1:η1 coordination mode for the bridging organic fragment, enforced by the rigid and dinucleating nature of the ligand utilized. Thus, the central π system remains unperturbed and accessible for subsequent reactivity and modification. This has been corroborated by addition of a fifth copper atom, giving rise to a pentacopper acetylide complex. This work may provide a new approach by which metal‐metal cooperativity can be exploited in the transformation of acetylide and diyne groups to a variety of substrates, or as a starting point for the controlled synthesis of copper(I) alkyne‐containing clusters.

Funder

U.S. Department of Energy

H2020 European Research Council

Publisher

Wiley

Subject

General Medicine

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