Neutral Unsymmetrical Coordinated Cyclophane Polymerization Catalysts

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Angewandte Chemie International Edition. Wiley. 2021, 60(34), pp. 18472-18477. ISSN 1433-7851. eISSN 1521-3773. Available under: doi: 10.1002/anie.202105401
Zusammenfassung

Cyclophane structures can control steric pressure in the otherwise open spaces of square-planar d 8 -metal catalysts. This elegant concept was so far limited to symmetrical coordinated metals. We report how a cyclophane motif can be generated in ligands that chelate via two different donors. An ancillary second imine in the versatile κ 2 - N,O -salicylaldiminato catalyst type enables ring closure via olefin metathesis and selective double bond hydrogenation to yield a 30-membered ring efficiently. Experimental and theoretical analyses show the ancillary imine is directed away from the active site and inert for catalysis. In ethylene polymerization the cyclophane catalyst is more active and temperature stable vs . an open structure reference, notably also in polar solvents. Increased molecular weights and decreased degrees of branching can be traced to an increased energy of sterically demanding transition states by the encircling cyclophane while chain propagation remains highly efficient.

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ISO 690SCHIEBEL, Eva, Maria VOCCIA, Laura FALIVENE, Inigo GÖTTKER-SCHNETMANN, Lucia CAPORASO, Stefan MECKING, 2021. Neutral Unsymmetrical Coordinated Cyclophane Polymerization Catalysts. In: Angewandte Chemie International Edition. Wiley. 2021, 60(34), pp. 18472-18477. ISSN 1433-7851. eISSN 1521-3773. Available under: doi: 10.1002/anie.202105401
BibTex
@article{Schiebel2021-08-16Neutr-53914,
  year={2021},
  doi={10.1002/anie.202105401},
  title={Neutral Unsymmetrical Coordinated Cyclophane Polymerization Catalysts},
  number={34},
  volume={60},
  issn={1433-7851},
  journal={Angewandte Chemie International Edition},
  pages={18472--18477},
  author={Schiebel, Eva and Voccia, Maria and Falivene, Laura and Göttker-Schnetmann, Inigo and Caporaso, Lucia and Mecking, Stefan}
}
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