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Dynamic Pdᴵᴵ/Cuᴵ Multimetallic Assemblies as Molecular Models to Study Metal-Metal Cooperation in Sonogashira Coupling

preprint
submitted on 19.12.2019 and posted on 23.12.2019 by Orestes Rivada-Wheelaghan, Aleix Comas Vives, Robert Fayzullin, Agustí Lledós, Julia Khusnutdinova
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 organometallic 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 both transmetalation and C-C elimination steps 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 in catalysis. 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. The phosphine ligand was shown to promote facile C-C elimination explained through NMR and DFT studies.

Funding

JSPS KAKENHI Grant Number 16F16038

MINECO CTQ2017-87889-P

MINECO PGC2018-100818-A-I00

Ramon y Cajal Fellowship RyC-2016-19930

History

Email Address of Submitting Author

juliak@oist.jp

Institution

Okinawa Institute of Science and Technology Graduate University

Country

Japan

ORCID For Submitting Author

0000-0002-5911-4382

Declaration of Conflict of Interest

No conflict of interests.

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