Well-Defined Pdn Clusters for Cross–Coupling and Hydrogenation Catalysis: New Opportunities for Catalyst Design

TY - JOUR

T1 - Well-Defined Pdn Clusters for Cross–Coupling and Hydrogenation Catalysis

T2 - New Opportunities for Catalyst Design

AU - Jeddi, Neda

AU - Scott, Neil W.J.

AU - Fairlamb, Ian J.S.

N1 - © 2022 The Authors

PY - 2022/9/9

Y1 - 2022/9/9

N2 - In recent studies it has been demonstrated that the privileged reactivity of higher order metal clusters can be exploited in widely applied catalytic processes, particularly cross-coupling reactions and hydrogenative transformations. Relatively small, well-defined Pdn clusters have been known since the 1960s. Unique reactivity, reaction (product) selectivity and catalyst behavior has been recently uncovered, from which there is much potential in catalyst design and application. Ligated Pdn clusters of a smaller size (where n is less than 6), may form upon degradation of mononuclear Pd species en route to larger particulate Pd (from <5 nanometer particles to large moribund forms in the >1 micrometer range). This review presents the catalytic applications of Pdn clusters. We pay particular attention to the underlying structure of the Pdn clusters, linked to their reactivity. A hypothesis that ligated Pdn clusters may constitute a mechanism by which higher order Pd species may form (as a bridging point for mono-ligated Pd species through to PdNPs) is further discussed. Where appropriate, we mention other catalytic reaction processes that complement the discussion focused on cross-coupling and hydrogenation processes.

AB - In recent studies it has been demonstrated that the privileged reactivity of higher order metal clusters can be exploited in widely applied catalytic processes, particularly cross-coupling reactions and hydrogenative transformations. Relatively small, well-defined Pdn clusters have been known since the 1960s. Unique reactivity, reaction (product) selectivity and catalyst behavior has been recently uncovered, from which there is much potential in catalyst design and application. Ligated Pdn clusters of a smaller size (where n is less than 6), may form upon degradation of mononuclear Pd species en route to larger particulate Pd (from <5 nanometer particles to large moribund forms in the >1 micrometer range). This review presents the catalytic applications of Pdn clusters. We pay particular attention to the underlying structure of the Pdn clusters, linked to their reactivity. A hypothesis that ligated Pdn clusters may constitute a mechanism by which higher order Pd species may form (as a bridging point for mono-ligated Pd species through to PdNPs) is further discussed. Where appropriate, we mention other catalytic reaction processes that complement the discussion focused on cross-coupling and hydrogenation processes.

KW - Palladium

KW - cross-coupling

KW - Catalysis

KW - Synthesis

KW - Organic

KW - Organometallic

KW - METAL CLUSTERS

KW - MECHANISM

UR - http://www.scopus.com/inward/record.url?scp=85138082695&partnerID=8YFLogxK

U2 - 10.1021/acscatal.2c03345

DO - 10.1021/acscatal.2c03345

M3 - Review article

AN - SCOPUS:85138082695

SN - 2155-5435

VL - 12

SP - 11615

EP - 11638

JO - ACS Catalysis

JF - ACS Catalysis

ER -