Document Type
Article
Publication Date
2025
DOI
10.1021/acs.organomet.5c00147
Publication Title
Organometallics
Volume
44
Issue
18
Pages
2016-2024
Abstract
Catalytic isomerization of alkenes has garnered interest for many years, but there are remaining challenges when it comes to thermodynamic selectivity and uncontrolled isomerization. Nonbiased substrates, be it sterically or thermodynamically, remain challenging for many catalysts, with a few examples available in the more modern literature. Herein, we present the controlled isomerization of linear alkenes with a cocatalytic mixture of commercially available catalyst and reagents: Grubbs I, tris(pentafluorophenyl)borane, and triethylsilane. DFT calculations indicate that an observed alkylidyne hydride intermediate is in rapid equilibrium with an alkylidene that binds the alkene substrate. This combination results in a pi-acidic metal and a hydridic H-B(C₆F₅)₃- counteranion to provide the controlled monoisomerization of aliphatic alkenes.
Rights
© 2025 The Authors.
This publication is licensed under a Creative Commons Attribution 4.0 International (CC-BY 4.0) license.
Original Publication Citation
Miller, P. D., Calkins, J. B., Bayse, C. A., & Bender, T. A. (2025). Metathesis or isomerization: Counteranion directed reactivity of Grubbs I. Organometallics, 44(18), 2016-2024. https://doi.org/10.1021/acs.organomet.5c00147
ORCID
0000-0002-0146-0346 (Miller), 0000-0002-3490-576X (Bayse)
Repository Citation
Miller, Paul D.; Calkins, Joe B.; Bayse, Craig A.; and Bender, Trandon A., "Metathesis or Isomerization: Counteranion Directed Reactivity of Grubbs I" (2025). Chemistry & Biochemistry Faculty Publications. 366.
https://digitalcommons.odu.edu/chemistry_fac_pubs/366
Experimental procedures, additional figures for mechanis and speciation evaluation, and analytical/characterization data
om5c00147_si_002.xyz (51 kB)
DFT coordinate data
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