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NMR chemical shift analysis decodes olefin oligo- and polymerization activity of d0 group 4 metal complexes [Chemistry]

The rational understanding and design of catalysts pose major challenges to chemists. While catalysts are involved in around 90% of industrial chemical processes, their discovery and development are usually based on screening and serendipity. Here, we show through a detailed analysis of the NMR chemical shift that the activity of olefin polymerization and oligomerization catalysts is directly related to the chemical shift of the carbon atom bound to the metal center. This relation is traced to specific frontier molecular orbitals, which induce π-character in the metal-alkyl bond, thereby favoring insertion. This result not only reveals a surprising analogy between olefin polymerization and metathesis, but also establishes chemical shift as a predictive descriptor for catalytic activity in these industrially relevant processes.

Authors:   Christopher P. Gordon; Satoru Shirase; Keishi Yamamoto; Richard A. Andersen; Odile Eisenstein; Christophe Copéret
Journal:   Proceedings of the National Academy of Sciences current issue
Volume:   115
edition:   26
Year:   2018
Pages:   E5867
DOI:   10.1073/pnas.1803382115
Publication date:   26-Jun-2018
Facts, background information, dossiers
  • Oligomerization
  • Metathesis
  • complexes
More about Proceedings of the National Academy of Sciences
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