Dynamic PdII/CuI Multimetallic Assemblies as Molecular Models to Study Metal–Metal Cooperation in Sonogashira Coupling |
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Authors: | Dr Orestes Rivada-Wheelaghan Dr Aleix Comas-Vives Dr Robert R Fayzullin Prof Agustí Lledós Prof Julia R Khusnutdinova |
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Institution: | 1. Coordination Chemistry and Catalysis Unit, Okinawa Institute of Science and Technology Graduate University, 1919-1 Tancha, Onna-son, Okinawa, 904-0495 Japan;2. Departament de Química, Universitat Autònoma de Barcelona, 08193 Bellaterra, Barcelona, Catalonia, Spain;3. Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, 8 Arbuzov Street, Kazan, 420088 Russian Federation |
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Abstract: | Cooperation between two different metals plays a crucial role in many synergistic catalytic reactions, such as the Sonogashira C?C cross-coupling reaction, where an interaction between the Pd and Cu centers is proposed in the transmetalation step. Although several heterobimetallic Pd/Cu complexes were proposed as structural models of the active species in Sonogashira coupling, the detailed understanding of the metal–metal cooperation in transmetalation is still lacking in current systems. In this work, we report a stepwise and systematic approach to building heteromultimetallic Pd/Cu assemblies as a tool to study metal–metal cooperativity. We obtained fully characterized Pd/Cu multimetallic assemblies that show reactivity in alkyne activation, formation of catalytically relevant aryl/acetylide species, and C?C elimination, serving as functional models for Sonogashira reaction intermediates. The combined experimental and DFT studies highlight the importance of ligand-controlled coordination geometry, metal–metal distances and dynamics of the multimetallic assembly for transmetalation step. |
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Keywords: | copper metal–metal cooperation metal–metal interactions palladium Sonogashira coupling |
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