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![[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
Cationic Copper Hydride Clusters Arising from Oxidation of (Ph3P)6Cu6H6
Shuo Liu1, Michael S Eberhart1, Jack R Norton1
1Department of Chemistry, Columbia University , 3000 Broadway, New York, New York 10027, United States.
Abstract:
Transfer of the first electron from (Ph3P)6Cu6H6 to Cp*2Fe+ is fast (k > 106 L·mol-1·s-1). Transfer of a second electron to the same oxidant has a much lower thermodynamic driving force and is considerably slower, with k = 9.29(4) × 103 L·mol-1·s-1. The second oxidation leads to the formation of [(Ph3P)6Cu6H5]+. The structure of [(Ph3P)6Cu6H5]+ has been confirmed by its conversion back to (Ph3P)6Cu6H6 and by microanalysis; X-ray diffraction shows that the complex is a bitetrahedron in the solid state. [(Ph3P)6Cu6H5]+ can also be prepared by treating (Ph3P)6Cu6H6 with MeOTf. With less than 1 equiv of Cp*2Fe+ as oxidant, (Ph3P)6Cu6H6 gives [(Ph3P)7Cu7H6]+ as the major product; X-ray diffraction shows a Cu6 octahedron with one face capped by an additional Cu. [(Ph3P)7Cu7H6]+ can also be prepared by treating (Ph3P)6Cu6H6 with [Cu(CH3CN)4]+ (along with 1 equiv of Ph3P), and can be converted back to (Ph3P)6Cu6H6 with base/H2.
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