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Updated: Dec 15, 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
Product inhibition in nucleophilic aromatic substitution through DPPPent-supported π-arene catalysis
Benjamin R J Mueller1, Nathan D Schley
1Department of Chemistry, Vanderbilt University, Nashville, Tennessee 37235, USA. nathan.schley@vanderbilt.edu.
Abstract:
Nucleophilic aromatic substitution (SNAr) of fluorobenzene by morpholine at a bis(diphenylphosphino)pentane-supported ruthenim complex is investigated as a model system for π-arene catalysis through the synthesis and full characterization of proposed intermediates. The SNAr step proceeds quickly at room temperature, however the product N-phenylmorpholine binds tightly to the ruthenium ion. In the case examined, the thermodynamics of arene binding favor product N-phenylmorpholine over fluorobenzene binding by a factor of 2000, corresponding to significant product inhibition. Observations of the catalyst resting state support this hypothesis and demonstrate an additive-controlled role for a previously-proposed ligand cyclometalation.
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