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Mechanism of ethylene dimerization catalyzed by Ti(OR')4/AlR3
journal contribution
posted on 2023-05-17, 14:26 authored by Suttil, JA, McGuinness, DSTi-alkoxide-based catalysts in combination with AlEt3 are responsible for the production of a significant proportion of the world's 1-butene supply, via the dimerization of ethylene. A metallacycle mechanism is normally presumed to operate with this system. However, despite its importance, the catalyst is not mechanistically well understood. The mechanism of dimerization has been studied through a series of C2H4/C2D4 co-oligomerization experiments and comparison of theoretical and experimental mass spectra. The results obtained show that the textbook metallacycle mechanism is most likely not responsible for dimerization with this catalyst. Instead, an excellent fit between the theoretical and experimental mass spectra is obtained when a conventional Cossee-type mechanism (insertion/β-hydride elimination) is modeled. The formation of both the primary product 1-butene and the secondary reaction products (ethylene/1-butene co-dimers) is best explained by this mechanism.
History
Publication title
OrganometallicsVolume
31Issue
19Pagination
7004-7010ISSN
0276-7333Department/School
School of Natural SciencesPublisher
Amer Chemical SocPlace of publication
1155 16Th St, Nw, Washington, USA, Dc, 20036Rights statement
Copyright 2012 American Chemical SocietyRepository Status
- Restricted