A Copper(I) Catenane Decorated Metal-Organic Layer as a Heterogenous Catalyst for Dehydrogenative Cross-Coupling

Area of Science:

• Catalysis
• Materials Science
• Supramolecular Chemistry

Background:

• Earth-abundant metals offer sustainable alternatives to precious metals for catalysis.
• Developing robust and reusable base metal catalysts is challenging due to fast ligand exchange.

Purpose of the Study:

• To develop a new heterogeneous catalyst using earth-abundant metals.
• To utilize catenane ligands for enhanced stability and selectivity in catalysis.
• To explore the potential of mechanical bonds in catalyst design.

Main Methods:

• Grafting catenane-coordinated Cu(I) complexes onto a 2D metal-organic layer (MOL).
• Evaluating the catalyst's performance in a model dehydrogenative C─O cross-coupling reaction.
• Comparing the catenane-based catalyst with a control catalyst using non-interlocked ligands.

Main Results:

• The Cu(I) catenane-grafted MOL catalyst demonstrated exclusive formation of the C─O coupled product.
• Control catalysis with non-interlocked ligands produced a C─C coupled by-product due to Cu(I) to Cu(II) oxidation.
• The mechanical bond in catenanes dynamically confined the coordination environment, stabilizing Cu(I).

Conclusions:

• Catenane coordination offers a new mechanism for kinetically stabilizing base metal catalysts.
• This approach leads to well-defined, active, and stable heterogeneous catalysts.
• The catenane strategy shows significant potential for developing advanced base metal catalysts for challenging reactions.