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Deactivation of Z-selective olefin metathesis catalyst via 1,2-sulfide shift

Lin, Janice and Montgomery, Timothy and Ahmed, Tonia and Grubbs, Robert and Houk, Kendall (2018) Deactivation of Z-selective olefin metathesis catalyst via 1,2-sulfide shift. In: 256th American Chemical Society National Meeting & Exposition, 19-23 August 2018, Boston, MA.

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Since the advent of olefin metathesis, stereoselective olefin metathesis catalysts have been sought after for use in academic and industrial applications. The most recently reported Ru-complex for Z-selective olefin metathesis features a catechothiolate ligand, and this catalyst has been shown to be esp. useful in ring-opening metathesis polymn. and ringopening-cross metathesis. However, this catalyst is prone to deactivation, as the electron-rich sulfur in the catechodithiolate ligand is susceptible to undergo a 1,2-shift to the neighboring electrophilic alkylidene, which effectively deactivates the catalyst. Hoveyda et al. used electroneg. groups on the dithiolate ligand to diminish the rate of the proposed isomerization and thus favor olefin metathesis towards high-value Z-allylic alc. products. However, a deeper study of the mechanism of deactivation and a further anal. of the electronic structure is necessary in order to understand the deactivation pathway and tune the catalyst to disfavor this 1,2-shift. Guided by expts., we present a computational study of the reaction pathway and present results on the electronic nature of the catalytically active species. We study the propensity for the catalytic species to undergo deactivation by analyzing the altered electronic structure that results from substrate coordination and alkylidene substitution. This work serves as grounds for understanding the reactivity of this new class of Ru-complexes and we propose design principles for further development of these catalysts for academic and industrial use.

Item Type:Conference or Workshop Item (Paper)
Related URLs:
URLURL TypeDescription Website
Montgomery, Timothy0000-0003-0975-088X
Grubbs, Robert0000-0002-0057-7817
Houk, Kendall0000-0002-8387-5261
Additional Information:© 2018 American Chemical Society.
Record Number:CaltechAUTHORS:20181109-112143731
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:90796
Deposited By: Tony Diaz
Deposited On:14 Nov 2018 19:17
Last Modified:03 Oct 2019 20:28

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