Catalysis with Palladium(I) Dimers

Angewandte Chemie International Edition, vol. 60, pp. 3355–3366

Abstract

Abstract Dinuclear Pd I complexes have found widespread applications as diverse catalysts for a multitude of transformations. Initially their ability to function as pre‐catalysts for low‐coordinated Pd 0 species was harnessed in cross‐coupling. Such Pd I dimers are inherently labile and relatively sensitive to oxygen. In recent years, more stable dinuclear Pd I −Pd I frameworks, which feature bench‐stability and robustness towards nucleophiles as well as recoverability in reactions, were explored and shown to trigger privileged reactivities via dinuclear catalysis. This includes the predictable and substrate‐independent, selective C−C and C−heteroatom bond formations of poly(pseudo)halogenated arenes as well as couplings of arenes with relatively weak nucleophiles, which would not engage in Pd 0 /Pd II catalysis. This Minireview highlights the use of dinuclear Pd I complexes as both pre‐catalysts for the formation of highly active Pd 0 and Pd II −H species as well as direct dinuclear catalysts. Focus is set on the mechanistic intricacies, the speciation and the impacts on reactivity.

Authors 4

1. Christoph Fricke Aachen Institute of Organic Chemistry

   RWTH Aachen University

   Affiliation as printed

   Institute of Organic Chemistry RWTH Aachen University Landoltweg 1 52074 Aachen Germany

   Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074 Aachen, Germany

   These authors contributed equally to this work

2. Theresa Sperger Aachen Institute of Organic Chemistry

   RWTH Aachen University

   Affiliation as printed

   Institute of Organic Chemistry RWTH Aachen University Landoltweg 1 52074 Aachen Germany

   Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074 Aachen, Germany

   These authors contributed equally to this work

3. Marvin Mendel Aachen Institute of Organic Chemistry

   RWTH Aachen University

   Affiliation as printed

   Institute of Organic Chemistry RWTH Aachen University Landoltweg 1 52074 Aachen Germany

   Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074 Aachen, Germany

4. Franziska Schoenebeck corresponding Aachen Institute of Organic Chemistry

   RWTH Aachen University

   Affiliation as printed

   Institute of Organic Chemistry RWTH Aachen University Landoltweg 1 52074 Aachen Germany

   Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074 Aachen, Germany