Mono- and bimetallic ethylene polymerization catalysts having an azanickellacyclopentene skeleton

A series of azanickellacyclopentene complexes having iodo, bromo, chloro, or triflate ligand on the Ni center were prepared, and are subjected to studies on ethylene polymerization catalysis. Activity of these mononuclear azanickellacyclopentene complexes was increased in the order, Ni–Cl < Ni–I ≈ Ni–Br < Ni–OTf; this is explained by the performance of (pseudo)halogeno ligand as a leaving group from the nickel center. Methylalminoxane (MAO) and inexpensive AlEt2Cl can be used as the cocatalyst. Mechanistic consideration suggested the involvement of neutral Ni-alkyl intermediates as proposed in the SHOP type catalytic system. Interestingly, the catalytic activity is significantly increased by incorporating the second metals into the diimino moiety of mononuclear complex. Two factors should be considered to explain this activity enhancement. One is the increased rigidity of the azanickellacyclopentene ligand backbone, and the other is the possibility of the presence of the two active centers in one molecule.

A series of azanickellacyclopentene complexes having iodo (1), bromo (3), chloro (4), or triflate ligand (2) on the Ni center were prepared, and are subjected to studies on ethylene polymerization catalysis. Activity of these mononuclear azanickellacyclopentene complexes was increased in the order, Ni–Cl < Ni–I ≈ Ni–Br < Ni–OTf. The formation of (hetero)bimetallic complexes, 5, 6, 7, and 8, were achieved by incorporating the second metals into the diimino moiety of 1 and 3. The catalytic activity for ethylene polymerization was significantly increased by using these (hetero)bimetallic complexes.Figure optionsDownload as PowerPoint slide