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Updated: Dec 8, 2025
![[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)
[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst
Published on: May 21, 2019
Hexanuclear Copper(I) Hydride from the Reduction-Induced Decarboxylation of a Dicopper(II) Formate
Jana Lücken1, Thomas Auth2, Sara Ida Mozzi1
1Institute of Inorganic Chemistry, University of Göttingen, Tammannstraße 4, D-37077 Göttingen, Germany.
Abstract:
Copper(I) hydride complexes represent a promising entry into formic acid dehydrogenation catalysis. Herein we present the spontaneous decarboxylation of a μ1,3-formate-bridged dicopper(II) complex (1) to a hexacopper(I) hydride cluster (2) upon reduction. Isotopic labeling studies revealed that both the H- and CO2 originate from the bound μ1,3-formate in 1, which represents a key step of the metal-mediated formic acid dehydrogenation. The full reaction equation for the conversion of 1 to 2 is established. The structure of 2 features two Cu3 triangles, each capped by a hydride ligand. Typical hydride reactivity of 2 is demonstrated by the addition of phenylacetylene, leading to the replacement of the hydrides by alkynide ligands -C≡CPh (3) while retaining the hexacopper(I) core. Temperature-dependent dynamic behavior in solution on the NMR time scale was observed for both 2 and 3, reflecting the rich structural landscape of the bis(pyrazolate)-bridged hexacopper(I) core (four isomers each for 2 and 3) predicted by DFT calculations.
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