Coordination Chemistry Reviews 253 (2009) 827–861 Contents lists available at ScienceDirect Coordination Chemistry Reviews journal homepage: www.elsevier.com/locate/ccr Review Metal catalysts for the vinyl/addition polymerization of norbornene Frederik Blank, Christoph Janiak ∗ Institut f¨ ur Anorganische und Analytische Chemie, Universit¨ at Freiburg, Albertstrasse 21, D-79104 Freiburg, Germany Contents 1. Introduction ......................................................................................................................................... 828 1.1. Modes of NB polymerization ................................................................................................................ 828 1.2. Vinyl norbornene copolymerization ........................................................................................................ 829 1.3. Substituted norbornenes .................................................................................................................... 829 1.4. Properties and applications of vinyl polynorbornene (PNB) ................................................................................ 830 2. Metal complexes for the vinyl NB polymerization ................................................................................................. 830 2.1. Cocatalysts ................................................................................................................................... 831 2.2. Titanium and zirconium catalysts ........................................................................................................... 831 2.3. Chromium catalysts ......................................................................................................................... 832 2.4. Iron catalysts ................................................................................................................................ 833 2.5. Cobalt catalysts .............................................................................................................................. 834 2.6. Nickel catalysts .............................................................................................................................. 835 2.6.1. N,N-Chelate and bis(N) ligands .................................................................................................... 836 2.6.2. N,O-(N,S-)Chelate ligands .......................................................................................................... 840 2.6.3. O,O-Chelate ligands ................................................................................................................ 846 2.6.4. Phosphane (arsane, stibane) ligands .............................................................................................. 847 2.6.5. Multidentate carbon-bonded ligands ............................................................................................. 849 2.7. Palladium catalysts .......................................................................................................................... 851 2.7.1. N,N-Chelate ligands ................................................................................................................ 851 2.7.2. N,O(N,S)-Chelate ligands ........................................................................................................... 852 2.7.3. O,O-Chelate ligands ................................................................................................................ 853 2.7.4. Phosphane ligands ................................................................................................................. 853 2.7.5. Homoleptic Pd complexes with chloro ligands .................................................................................... 855 2.7.6. Multidentate carbon-bonded ligands ............................................................................................. 856 2.8. Copper catalysts ............................................................................................................................. 856 3. Supported catalysts ................................................................................................................................. 857 4. Di- and multinuclear metal complexes ............................................................................................................. 858 5. Activity comparison ................................................................................................................................. 858 6. Conclusions ......................................................................................................................................... 859 References .......................................................................................................................................... 859 Abbreviations: n Bu, n-butyl, C4H9; t Bu, tert-butyl, Me3C; COC, cycloolefin copolymer; Cp, cyclopentadienyl; MAO, methylalumoxane; dMAO, dried MAO; MMAO, modified MAO; dppb, diphenylphosphinobutane; dppe, diphenylphosphinoethane; dppp, diphenylphosphino-propane; dpppt, diphenylphos- phinopentane; Et, ethyl, C2H5; Me, methyl, CH3; NB, norbornene, C7H10; NMR, nuclear magnetic resonance; ODCB, ortho-dichlorobenzene, C6H4Cl2; PNB, poly(norbornene); py, pyridine, C5H5N; Ph, phenyl, C6H5; i Pr, iso-propyl, C3H7, (CH3)2CH-; ROMP, ring opening metathesis polymerization; TOPAS, thermo- plastic olefin polymer of amorphous structure. ∗ Corresponding author. Tel.: +49 761 2036127; fax: +49 761 2036147. E-mail address: janiak@uni-freiburg.de (C. Janiak). 0010-8545/$ – see front matter © 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.ccr.2008.05.010