LAUSR

Abstract A series of four NNN-pyridine based ligands of the general form: pyCH2N(R)CH2py {R = propyl, tert-butyl, cyclohexyl and phenyl; py = pyridine} were synthesised and characterised. Complexation of each ligand to CoCl2·6H2O afforded new Co(II) complexes [Co{pyCH2N(R)CH2py}Cl2] (R = C3H7 (1), C(CH3)3 (2), C6H11 (3) and C6H5 (4)). Single crystal X-ray diffraction data confirmed that complex 1 crystallised as a mononuclear unit and was characterised by a distorted trigonal bipyramidal arrangement of ligands around Co. As catalysts in the oxidation of n-octane using t-BuOOH as oxidant, 2 (10% product yield) was found to be most efficient and the selectivity over 1–4 was predominantly towards 2-octanol, after reduction of alkylhydroperoxides by PPh3. All catalysts were significantly more active in the activation of n-octane using hydrogen peroxide, with a yield of 45% observed over catalyst 3. Furthermore, with H2O2, all catalysts produced a high concentration of alkylhydroperoxides, with catalyst 4 giving up to 91% alcohols after workup. TONs of up to 1100 were achieved over the Co/H2O2 systems.