Dynamic PdII /CuI Multimetallic Assemblies as Molecular Models to Study Metal-Metal Cooperation in Sonogashira Coupling.
Chemistry
; 26(53): 12168-12179, 2020 Sep 21.
Article
em En
| MEDLINE
| ID: mdl-32427376
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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01-internacional
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MEDLINE
Idioma:
En
Ano de publicação:
2020
Tipo de documento:
Article