Operando Studies of Palladium-Catalysed Cross-Coupling Surface Chemistry
Lead Research Organisation:
University of York
Department Name: Chemistry
Abstract
Pd-catalysed cross-coupling reactions represent key technologies employed within academia and industry, however the fine chemicals sector urgently needs new catalytic systems for large-scale, continuous processing. This proposal underpins the development of alternative, heterogeneous Pd-catalysed processes to meet this demand. Commercialization of such catalytic clean technologies awaits detailed knowledge of their optimal formulation and associated reaction conditions. This information in turn requires insight into both the mechanisms of such surface reactions and their associated deactivation pathways in order to control both activity and selectivity (homo- versus cross-coupling). Here we propose to obtain microscopic-level understanding of Heck and Suzuki-Miyaura chemistry over well-defined model palladium surfaces through the use of operando surface spectroscopies and mechanistic reaction probes. We have recently pioneered the application of in-situ, X-ray photoelectron spectroscopy for real-time investigations of industrially significant, surface catalysed processes including alkyne trimerisation, C-H activation and VOC destruction. These methodologies will also allow us to determine whether heterogeneously catalysed cross-coupling shares common reaction intermediates and rate-limiting steps with its more conventional homogeneous counterparts. The intellectual output from this project will be invaluable in designing a new toolbox of high performance dispersed Pd catalysts that will revolutionise organic synthetic chemistry.
Publications
Naughton J
(2011)
Metastable De-excitation Spectroscopy and Density Functional Theory Study of the Selective Oxidation of Crotyl Alcohol over Pd(111)
in The Journal of Physical Chemistry C
Lee A
(2007)
Hydrodebromination of Bromobenzene over Pt(111)
in The Journal of Physical Chemistry C
Lee A
(2007)
Selective Oxidation of Crotyl Alcohol over Pd(111)
in The Journal of Physical Chemistry C
Zeinalipour-Yazdi C
(2016)
CO adsorption over Pd nanoparticles: A general framework for IR simulations on nanoparticles
in Surface Science
Naughton J
(2010)
Reactivity of crotonaldehyde and propene over Au/Pd(111) surfaces.
in Physical chemistry chemical physics : PCCP
Zeinalipour-Yazdi CD
(2014)
Impact of co-adsorbed oxygen on crotonaldehyde adsorption over gold nanoclusters: a computational study.
in Physical chemistry chemical physics : PCCP
Sehnal P
(2009)
Heteroaromatic Analogues of Dibenzylideneacetone (dba) and Pd 0 2 (het-dba) 3 Complexes: Effect of a Thienyl Moiety on the Reactivity of Pd 0 (? 2 -th n -dba)(PPh 3 ) 2 /Pd 0 (PPh 3 ) 2 ( n = 1 or 2) and Pd 0 (? 2 -th 2 -dba)(dppe)/Pd 0 (dppe) in Oxidative Addition Reactions with Iodobenzene
in Organometallics
Fairlamb I
(2007)
In - Silico Prediction of Pd-Catalyzed Cross-Coupling Processes: Dibenzylidene Acetone (dba) Ligand Control
in Organometallics
Lee A
(2011)
In-situ X-ray Studies of Clean Catalytic Technologies
in MRS Proceedings
Description | The first direct evidence for surface catalysed C-C bond-forming reactions (Suzuki-Miyaura) over Pd nanoparticles was discovered through dynamic X-ray spectroscopic studies of tunable palladium nanoparticles and single crystals. |
Exploitation Route | The time-resolved methodologies developed at the Elettra and ESRF synchrotrons have wide application for structure-reactivity studies across the physical sciences, and are broadly applicable to a range of commercially important solution phase catalytic transformations employed across the fine chemical and pharmaceutical sectors. New opportunities have been identifed for the synthesis of nanoparticulate Pd catalysts to effect C-C cross-coupling chemistry under mild conditions, opening the possibility for intensified processing under continuous flow. |
Sectors | Chemicals,Pharmaceuticals and Medical Biotechnology |
Description | Synchtrotron studies of nanostructured materials |
Organisation | Elettra Sincrotrone Trieste |
Country | Italy |
Sector | Academic/University |
PI Contribution | New research areas in catalysis and materials science developed resulting in numerous jointly authored publications over 17 years. |
Collaborator Contribution | Access to synchtrotron facilities and training of 8 PhD students and PDRAs |
Impact | Joint publications, contributions to annual highlights, invited seminar and Fonda-Fasella 2004 award |