Article
Ethylene dimerization and oligomerization using Bis(phosphino)boryl supported Ni complexes
Author/s | Kong, Fanji
Ríos Moreno, Pablo Hauck, Conner Fernández de Córdova, Francisco José Dickie, Diane A. Habgood, Laurel G. Rodríguez, Amor Gunnoe, T. Brent |
Department | Universidad de Sevilla. Departamento de Química Inorgánica |
Publication Date | 2022-12-21 |
Deposit Date | 2024-09-19 |
Published in |
|
Abstract | We report the dimerization and oligomerization of ethylene using bis(phosphino)boryl supported Ni(II) complexes as catalyst precursors. By using alkylaluminum(III) compounds or other Lewis acid additives, Ni(II) complexes ... We report the dimerization and oligomerization of ethylene using bis(phosphino)boryl supported Ni(II) complexes as catalyst precursors. By using alkylaluminum(III) compounds or other Lewis acid additives, Ni(II) complexes of the type (RPBP)NiBr (R = tBu or Ph) show activity for the production of butenes and higher olefins. Optimized turnover frequencies of 640 molethylene·molNi–1·s–1 for the formation of butenes with 41(1)% selectivity for 1-butene using (PhPBP)NiBr, and 68 molethylene·molNi–1·s–1 for butenes production with 87.2(3)% selectivity for 1-butene using (tBuPBP)NiBr, have been demonstrated. With methylaluminoxane as a co-catalyst and (tBuPBP)NiBr as the precatalyst, ethylene oligomerization to form C4 through C20 products was achieved, while the use of (PhPBP)NiBr as the pre-catalyst retained selectivity for C4 products. Our studies suggest that the ethylene dimerization is not initiated by Ni hydride or alkyl intermediates. Rather, our studies point to a mechanism that involves a cooperative B/Ni activation of ethylene to form a key 6-membered borametallacycle intermediate. Thus, a cooperative activation of ethylene by the Ni–B unit of the (RPBP)Ni catalysts is proposed as a key element of the Ni catalysis. |
Funding agencies | National Science Foundation (NSF). United States University of Virginia Ministerio de Economía y Competitividad (MINECO). España Junta de Andalucía Consejo Superior de Investigaciones Científicas (CSIC) |
Project ID. | CHE-2102433
CHE-2018870 PID2019 109312GB-IOO RED2018-102387-T PY20_00513 AEPP-CTQ2016-76267-P |
Citation | Kong, F., Ríos Moreno, P., Hauck, C., Fernández de Córdova, F.J., Dickie, D.A., Habgood, L.G.,...,Gunnoe, T.B. (2022). Ethylene dimerization and oligomerization using Bis(phosphino)boryl supported Ni complexes. Journal of the American Chemical Society, 145 (1), 179-193. https://doi.org/10.1021/jacs.2c09471. |
Files | Size | Format | View | Description |
---|---|---|---|---|
Ethylene Dimerization_C.pdf | 1.986Mb | [PDF] | View/ | Versión aceptada |