Issue 23, 2019

Catalytic activation of ethylene C–H bonds on uniform d8 Ir(i) and Ni(ii) cations in zeolites: toward molecular level understanding of ethylene polymerization on heterogeneous catalysts

Abstract

The homolytic activation of the strong C–H bonds in ethylene is demonstrated, for the first time, on d8 Ir(I) and Ni(II) single atoms in the cationic positions of zeolites H-FAU and H-BEA under ambient conditions. The oxidative addition of C2H4 to the metal center occurs with the formation of a d6 metal vinyl hydride, explaining the initiation of the olefin-polymerization cycle on d8 M(I/II) sites in the absence of pre-existing M–H bonds. Under mild reaction conditions (80–220 °C, 1 bar), the catalytic dimerization to butenes and dehydrogenative coupling of ethylene to butadiene occurs over these catalysts. 1-Butene is not converted to butadiene under the reaction conditions applied. Post-reaction characterization of the two materials reveals that the active metal cations remain site-isolated whereas deactivation occurs due to the formation of carbonaceous deposits on the zeolites. Our findings have significant implications for the molecular level understanding of ethylene conversion and the development of new ways to functionalize C–H bonds under mild conditions.

Graphical abstract: Catalytic activation of ethylene C–H bonds on uniform d8 Ir(i) and Ni(ii) cations in zeolites: toward molecular level understanding of ethylene polymerization on heterogeneous catalysts

Supplementary files

Article information

Article type
Paper
Submitted
20 ⵢⵓⵍ 2019
Accepted
16 ⴽⵜⵓ 2019
First published
22 ⴽⵜⵓ 2019

Catal. Sci. Technol., 2019,9, 6570-6576

Author version available

Catalytic activation of ethylene C–H bonds on uniform d8 Ir(I) and Ni(II) cations in zeolites: toward molecular level understanding of ethylene polymerization on heterogeneous catalysts

N. R. Jaegers, K. Khivantsev, L. Kovarik, D. W. Klas, J. Z. Hu, Y. Wang and J. Szanyi, Catal. Sci. Technol., 2019, 9, 6570 DOI: 10.1039/C9CY01442J

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements