title: Chemical reactions at the graphitic step-edge: changes in product distribution of catalytic reactions as a tool to explore the environment within carbon nanoreactors.
abstract: A series of explorative cross-coupling reactions have been developed to investigate the local nanoscale environment around catalytically active Pd(ii)complexes encapsulated within hollow graphitised nanofibers (GNF). Two new fullerene-containing and fullerene-free Pd(ii)Salen catalysts have been synthesised, and their activity and selectivity towards different substrates has been explored in nanoreactors. The catalysts not only show a significant increase in activity and stability upon heterogenisation at the graphitic step-edges inside the GNF channel, but also exhibit a change in selectivity affected by the confinement which alters the distribution of isomeric products of the reaction. Furthermore, the observed selectivity changes reveal unprecedented details regarding the location and orientation of the catalyst molecules inside the GNF nanoreactor, inaccessible by any spectroscopic or microscopic techniques, thus shedding light on the precise reaction environment inside the molecular catalyst-GNF nanoreactor.
authors.affiliation: School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD, UK. maria.lebedeva@materials.ox.ac.uk and Department of Materials, University of Oxford, 16 Parks Road, Oxford, OX1 3PH, UK.
authors.forename: Maria A
authors.initials: MA
authors.lastname: Lebedeva
authors.affiliation: School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD, UK. maria.lebedeva@materials.ox.ac.uk and School of Chemistry, University of Leeds, Leeds, LS2 9JT, UK.
authors.forename: Thomas W
authors.initials: TW
authors.lastname: Chamberlain
authors.affiliation: School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD, UK. maria.lebedeva@materials.ox.ac.uk.
authors.forename: Alice
authors.initials: A
authors.lastname: Thomas
authors.affiliation: School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD, UK. maria.lebedeva@materials.ox.ac.uk.
authors.forename: Bradley E
authors.initials: BE
authors.lastname: Thomas
authors.affiliation: School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD, UK. maria.lebedeva@materials.ox.ac.uk.
authors.forename: Craig T
authors.initials: CT
authors.lastname: Stoppiello
authors.affiliation: Institute of Mechanics of Ural Branch of Russian Academy of Sciences, T. Baramzinoy St., 34, Izhevsk, 426067, Russian Federation.
authors.forename: Evgeniya
authors.initials: E
authors.lastname: Volkova
authors.affiliation: Institute of Mechanics of Ural Branch of Russian Academy of Sciences, T. Baramzinoy St., 34, Izhevsk, 426067, Russian Federation.
authors.forename: Mikhail
authors.initials: M
authors.lastname: Suyetin
authors.affiliation: School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD, UK. maria.lebedeva@materials.ox.ac.uk and Nanoscale and Microscale Research Centre, University of Nottingham, University Park, Nottingham, NG7 2RD, UK.
authors.forename: Andrei N
authors.initials: AN
authors.lastname: Khlobystov