TY - CHAP
T1 - Fundamental Pd0/PdII redox steps in cross-coupling reactions
T2 - homogeneous, hybrid homogeneous-heterogeneous to heterogeneous mechanistic pathways for C-C couplings
AU - Fairlamb, Ian J.S.
AU - Lee, Adam F.
PY - 2013
Y1 - 2013
N2 - 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.
AB - 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.
UR - http://pubs.rsc.org/en/Content/Chapter/9781849737166-00072/978-1-84973-716-6#!divabstract
U2 - 10.1039/9781849737166-00072
DO - 10.1039/9781849737166-00072
M3 - Chapter (peer-reviewed)
SN - 978-1-84973-570-4
VL - 11
T3 - RSC Catalysis Series
BT - C–H and C–X bond functionalization
A2 - Ribas, Xavi
PB - Royal Society of Chemistry
CY - Cambridge (UK)
ER -