The Effects of Carbon Nanoreactor Diameter and Internal Structure on the Pathways of Catalytic Chemical Transformations

W.A. Solomonsz, G.A. Rance, A.N. Khlobystov
University of Nottingham, UK

Keywords: carbon nanotubes, nanoreactors, confinement, regioselectivity

Summary:

Molecular confinement inside hollow nanoscale containers permits a unique opportunity to study the influence of intense spatial restriction on the structural and chemical properties of individual molecules and kinetics and selectivity of preparative chemical reactions. In our previous studies, we have selectively immobilised a range of late transition metal catalysts within carbon nanoreactors and applied these novel catalytic nanocontainers in a range of preparative chemical transformations and have observed unprecedented control of selectivity, activity and recyclability as a direct consequence of nanoscale confinement. In our current studies, we have explored the effects of carbon nanoreactor diameter and internal structure on the properties of confined catalytic chemical transformations. We have shown that somewhat surprisingly the widest nanoreactors change the reaction pathway most significantly, which is attributed to the graphitic step-edges inside nanoreactors providing effective anchoring points for the catalyst and creating local environments with greatly altered concentrations of reactants as compared to bulk solution. These enhanced local concentrations of reactants can be harnessed for both small molecule and oligomeric synthesis and have led to unprecedented control of the formation of products inaccessible by other means.