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Selectivity Effects on N, N, N′-Cobalt Catalyzed Ethylene Dimerization/Trimerization Dictated through Choice of Aluminoxane Cocatalyst

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journal contribution
posted on 2019-04-17, 13:21 authored by Yongfeng Huang, Randi Zhang, Tongling Liang, Xinquan Hu, Gregory A. Solan, Wen-Hua Sun
The cobalt(II) chloride complexes, [2-(C 7 H 4 N 2 H)-8-(ArN)C 10 H 8 N]CoCl 2 (Ar = 2,6-Me 2 C 6 H 3 Co1; 2,6-Et 2 C 6 H 3 Co2; 2,6-i-Pr 2 C 6 H 3 Co3; 2,4,6-Me 3 C 6 H 2 Co4; 2,6-Et 2 -4-MeC 6 H 2 Co5; 2,4,6-t-Bu 3 C 6 H 2 Co6), have each been prepared by a one-pot template reaction of 2-benzoimidazolyl-5,6,7-trihydroquinolin-8-one with the corresponding aniline in the presence of cobalt dichloride. The molecular structures of the methanol adducts, Co1(HOMe) and Co4(HOMe), reveal distorted octahedral geometries that self-assemble to form networks based on NH···Cl and OH···Cl intermolecular hydrogen bonding interactions. On activation with methylaluminoxane (MAO), all six cobalt complexes catalyzed ethylene dimerization with a high selectivity for 1-butene. By marked contrast, with modified methylaluminoxane (MMAO), products the result of ethylene dimerization and trimerization were observed with a bias toward the C 6 products (up to 49% 1-hexene). In general, the MMAO-promoted oligomerizations display higher catalytic activities with mesityl-containing Co4 the stand-out performer [7.60 × 10 5 g·mol -1 (Co) h -1 at 50 °C].

Funding

This work was supported by the National Natural Science Foundation of China (No. 21871275). G.A.S. thanks the Chinese Academy of Sciences for a President’s International Fellowship for Visiting Scientists.

History

Citation

Organometallics, 2019, 38(5), pp. 1143-1150

Author affiliation

/Organisation/COLLEGE OF SCIENCE AND ENGINEERING/Department of Chemistry

Version

  • AM (Accepted Manuscript)

Published in

Organometallics

Publisher

American Chemical Society

issn

0276-7333

eissn

1520-6041

Copyright date

2019

Publisher version

https://pubs.acs.org/doi/10.1021/acs.organomet.8b00924

Notes

The file associated with this record is under embargo until 12 months after publication, in accordance with the publisher's self-archiving policy. The full text may be available through the publisher links provided above.;CCDC 1871156 and 1871157 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing data_request@ccdc.cam.ac.uk, or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

Language

en

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