Fundamental Pd0/PdII redox steps in cross-coupling reactions: homogeneous, hybrid homogeneous-heterogeneous to heterogeneous mechanistic pathways for C-C couplings

Ian J.S. Fairlamb, Adam F. Lee

Research output: Chapter in Book/Report/Conference proceedingChapter (peer-reviewed)

Abstract

C–C bond-forming, cross-coupling reactions of organohalides with nucleophilic compounds, catalysed by palladium, are amongst the most important chemical reactions available to the synthetic chemist. The intimate mechanisms of these reactions, involving Pd0/PdII redox steps, have been of great historical interest and continue to be so. The myriad of possible mechanisms is reviewed in this chapter. The interplay of mononuclear Pd species with higher order Pd species, e.g. nanoclusters/nanoparticles are considered as being equally important in cross-coupling reaction mechanisms. A focus is placed on trichotomic behaviour of cross-coupling catalytic manifolds, from homogeneous to hybrid homogeneous–heterogeneous to truly heterogeneous behaviour. For the latter, surface chemistry and metal atom leaching (and various experimental techniques) are broadly discussed. It is now clear that mechanism for general cross‐coupling reactions, that is as presented to undergraduate students studying Chemistry degrees across the world, is undoubtedly more complex than first thought. New opportunities for catalyst design have therefore emerged in the area of Pd nanoparticles and nanocatalysis, with some wonderful applications especially in chemical biology, providing a snapshot of what the future might hold.
Original languageEnglish
Title of host publicationC–H and C–X bond functionalization
Subtitle of host publicationtransition metal mediation
EditorsXavi Ribas
Place of PublicationCambridge (UK)
PublisherRoyal Society of Chemistry
Volume11
ISBN (Electronic)978-1-84973-716-6
ISBN (Print)978-1-84973-570-4
DOIs
Publication statusPublished - 2013

Publication series

NameRSC Catalysis Series
PublisherRoyal Society of Chemistry
Volume11
ISSN (Print)1757-6725

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    Fairlamb, I. J. S., & Lee, A. F. (2013). Fundamental Pd0/PdII redox steps in cross-coupling reactions: homogeneous, hybrid homogeneous-heterogeneous to heterogeneous mechanistic pathways for C-C couplings. In X. Ribas (Ed.), C–H and C–X bond functionalization : transition metal mediation (Vol. 11). (RSC Catalysis Series; Vol. 11). Royal Society of Chemistry. https://doi.org/10.1039/9781849737166-00072