Substituent Effects in (k2-N,O)-Salicylaldiminato Nickel(II)-Methyl Pyridine Polymerization Catalysts : Terphenyls Controlling Polyethylene Microstructures

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2007
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Wehrmann, Peter
Röhr, Caroline
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Organometallics. 2007, 26(9), pp. 2348-2362. ISSN 0276-7333. eISSN 1520-6041. Available under: doi: 10.1021/om0611498
Zusammenfassung

A series of (k2-N,O)-salicylaldiminato Ni(II)-methyl pyridine complexes 7-pyr and 8-pyr derived from 3,5-diiodosalicyaldehyde (3a) and 3-(9-anthryl)salicylaldehyde (3b), and terphenylamines 2,6-(3,5- R-4-R-C6H2)2C6H3-NH2 (4a, R=CF3, R'= H; 4b, R=tBu, R'=H; 4c, R=tBu, R'=OH; 4d, R=Me, R'=H; 4e, R=Me, R'=MeO; 4f, R=MeO, R'=H; 4g, R=MeO, R'=MeO), was prepared by reaction of the respective salicylaldimine (5a-f, 6a-g) with [(tmeda)Ni(CH3)2] (tmeda) N,N,N,N-tetramethylethylenediamine) or [(pyridine)2Ni(CH3)2]. Complexes 7-pyr and 8-pyr are highly active single component catalysts for the polymerization of ethylene, producing a wide range of different polyethylene microstructures. While comparable complexes derived from 3a, 3b, 5-nitrosalicylaldehyde, 3-tertbutylsalicylaldehyde,3,5-[3,5-(CF3)2C6H3]2-salicylaldehyde, and 2,6-[3,5-(CF3)2C6H3]2C6H3-NH2 afford polyethylenes with similar degrees of branching, variation of the terphenyl moieties in complexes 7-pyr and 8-pyr allows access to a wide range of polyethylene microstructures under identical reaction conditions. The X-ray diffraction analyses of complexes 7b-pyr and 8f-pyr are reported.

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ISO 690GÖTTKER-SCHNETMANN, Inigo, Peter WEHRMANN, Caroline RÖHR, Stefan MECKING, 2007. Substituent Effects in (k2-N,O)-Salicylaldiminato Nickel(II)-Methyl Pyridine Polymerization Catalysts : Terphenyls Controlling Polyethylene Microstructures. In: Organometallics. 2007, 26(9), pp. 2348-2362. ISSN 0276-7333. eISSN 1520-6041. Available under: doi: 10.1021/om0611498
BibTex
@article{GottkerSchnetmann2007Subst-9696,
  year={2007},
  doi={10.1021/om0611498},
  title={Substituent Effects in (k2-N,O)-Salicylaldiminato Nickel(II)-Methyl Pyridine Polymerization Catalysts : Terphenyls Controlling Polyethylene Microstructures},
  number={9},
  volume={26},
  issn={0276-7333},
  journal={Organometallics},
  pages={2348--2362},
  author={Göttker-Schnetmann, Inigo and Wehrmann, Peter and Röhr, Caroline and Mecking, Stefan}
}
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    <dcterms:abstract xml:lang="eng">A series of (k2-N,O)-salicylaldiminato Ni(II)-methyl pyridine complexes 7-pyr and 8-pyr derived from 3,5-diiodosalicyaldehyde (3a) and 3-(9-anthryl)salicylaldehyde (3b), and terphenylamines 2,6-(3,5- R-4-R-C6H2)2C6H3-NH2 (4a, R=CF3, R'= H; 4b, R=tBu, R'=H; 4c, R=tBu, R'=OH; 4d, R=Me, R'=H; 4e, R=Me, R'=MeO; 4f, R=MeO, R'=H; 4g, R=MeO, R'=MeO), was prepared by reaction of the respective salicylaldimine (5a-f, 6a-g) with [(tmeda)Ni(CH3)2] (tmeda) N,N,N,N-tetramethylethylenediamine) or [(pyridine)2Ni(CH3)2]. Complexes 7-pyr and 8-pyr are highly active single component catalysts for the polymerization of ethylene, producing a wide range of different polyethylene microstructures. While comparable complexes derived from 3a, 3b, 5-nitrosalicylaldehyde, 3-tertbutylsalicylaldehyde,3,5-[3,5-(CF3)2C6H3]2-salicylaldehyde, and 2,6-[3,5-(CF3)2C6H3]2C6H3-NH2 afford polyethylenes with similar degrees of branching, variation of the terphenyl moieties in complexes 7-pyr and 8-pyr allows access to a wide range of polyethylene microstructures under identical reaction conditions. The X-ray diffraction analyses of complexes 7b-pyr and 8f-pyr are reported.</dcterms:abstract>
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