Zhenzhong Hu <zhenzhong.hu@mun>, Fran M. Kerton*<fkerton@mun>

1. Cloud point data for L1 () and [Cu(L2)](PF6) (▲) in carbon dioxide. L2 is miscible in liquid CO2. [Cu(L1)](PF6) is insoluble at Ts and Ps studied. • L2 titrated with Cu(I) reagent (L1 behaves similarly) • MLCT band max. intensity reached at a ratio CM/CP= 1 • Metallocyclopolymer is characterised by NMR, FT-IR, GPC, CHN, MALDI-TOF MS Efficient aerobic oxidation of alcohols using CuBr2 and a series of α- pyridyl-imine terminated polydimethylsiloxane ligands Zhenzhong Hu<zhenzhong.hu@mun.ca>, Fran M. Kerton*<fkerton@mun.ca> Department of Chemistry, Memorial University of Newfoundland, St. John’s, NL, Canada, A1B 3X7 Introduction From the point of view of Green Chemistry, polymer-based catalysts are very environmentally friendly. These catalysts can be used and recycled in green solvents such as liquid polymers and supercritical carbon dioxide. They can also be very selective. In our recent studies, a series of α-pyridyl-imine terminated polydimethylsiloxane ligands have been synthesized and characterized.Itisinteresting that these carbondioxide miscible ligands form metallocyclic complexes when coordinated with copper(I) salt. Meanwhile, they provide perfect binding sites for copper (II) ions which then work as catalysts for more efficient aerobic oxidations of primary and secondary alcohols. Ligand Synthesis Solubility in Supercritical CO2 Coordination Chemistry Aerobic oxidation of selected alcohols with in situ made TEMPO/[Cu]/L1 system Summary • α-w Pyridyl-imine terminated PDMS compounds have been prepared and characterised. • Coordination chemistry with Cu(I) shows the formation of [1+1] metallocycles. • The TEMPO/[CuBr2]/L1 catalytic system is very effective for the aerobic oxidation of alcohols. • Future studies will involve the study of catalytic reaction mechanism and the recycling of the catalyst. • Attempts will also be made to obtain further evidence for the structures of these metallocyclic polymers. [a] GC conversion, selectivity > 99%; [b] Reaction temperature = 45 oC, using compressed air; [c] Reaction time = 48 h Acknowledgements; Prof. Christopher M. Kozak; Green Chemistry and Catalysis Group; Dr. Celine Schneider ; C-CART (Brent, Linda & Julie); Chemistry Department, Memorial University