Synthesis, characterisation and solid state structures of α-diimine cobalt(II) complexes: Ethylene polymerisation tests

A series of cobalt(II) compounds of the type [CoX2(α-diimine)] were synthesised by direct reaction of anhydrous CoCl2 or CoI2 and the corresponding α-diimine ligand, in CH2Cl2: [CoI2(o,o′,p-Me3C6H2-DAB)] (1), [CoI2(o,o′-iPr2C6H3-DAB)] (2), (where Ar-DAB = 1,4-bis(aryl)-2,3-dimethyl-1,4-diaza-1,3-butadiene), and [CoCl2(o,o′,p-Me3C6H2-BIAN)] (3), [CoCl2(o,o′-iPr2C6H3-BIAN)] (4), and [CoI2(o,o′-iPr2C6H3-BIAN)] (5) (where Ar-BIAN = bis(aryl)acenaphthenequinonediimine). All compounds were characterised by elemental analyses, IR, mass spectrometry, and X-ray diffraction whenever possible. The crystal structures of compounds 2–4 showed, in all cases, distorted tetrahedral geometries about the Co, built by two halogen atoms and two nitrogen atoms of the α-diimine ligand. Compounds 3 and 4, as well as [CoCl2(o,o′,p-Me3C6H2-DAB)] (1a), and [CoCl2(o,o′-iPr2C6H3-DAB)] (2a), were activated by methylaluminoxane (MAO) and tested as catalysts for ethylene polymerisation, showing low catalytic activities. Selected polyethylene (PE) samples were characterised by 1H and 13C NMR and FT-IR spectroscopies, and by differential scanning calorimetry (DSC), revealing branching microstructures (2.5–5.5%).