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Effects of alkyl group and NHC ligand variation with ruthenium-based olefin metathesis catalysts bearing chelating ortho-alkoxy benzylidenes

Luo, Shaoxiong and Engle, Keary and Liu, Peng and Dong, Xiaofei and Taylor, Buck and Takase, Michael and Houk, Kendall and Grubbs, Robert (2016) Effects of alkyl group and NHC ligand variation with ruthenium-based olefin metathesis catalysts bearing chelating ortho-alkoxy benzylidenes. In: 252nd American Chemical Society National Meeting & Exposition, 21-25 August 2016, Philadelphia, PA. http://resolver.caltech.edu/CaltechAUTHORS:20160913-122947066

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Abstract

A series of second-generation ruthenium olefin metathesis catalysts was investigated using a combination of reaction kinetics, X-ray crystallog., NMR spectroscopy, and DFT calcns. in order to det. the relationship between the structure of the chelating ortho-alkoxybenzylidene and the obsd. initiation rate. Included in this series were twenty new catalysts contg. an array of ortho-alkoxy benzylidenes and NHC ligands. The initiation rates of this series of catalysts were detd. using a UV/Vis assay. All new catalysts were obsd. to be faster-initiating than the corresponding isopropoxy control, and the dicyclohexylmethyl catalyst was found to be among the fastest-initiating Hoveyda-type catalysts reported to date. Anal. of the X-ray structures and computed energy-minimized structures of these catalysts revealed no correlation between Ru-O bond length and Ru-O bond strength. On the other hand, the initiation rate was found to correlate strongly with the computed Ru-O bond strength. This latter finding enables both rationalization and prediction of catalyst initiation through calcn. of a single thermodn. parameter, in which no assumptions about mechanism of the initiation step are made.


Item Type:Conference or Workshop Item (Paper)
Related URLs:
URLURL TypeDescription
https://www.acs.org/content/acs/en/meetings/fall-2016.htmlOrganizationConference Website
ORCID:
AuthorORCID
Engle, Keary0000-0003-2767-6556
Liu, Peng0000-0002-8188-632X
Houk, Kendall0000-0002-8387-5261
Grubbs, Robert0000-0002-0057-7817
Additional Information:© 2016 American Chemical Society.
Record Number:CaltechAUTHORS:20160913-122947066
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20160913-122947066
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:70311
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:30 Sep 2016 00:01
Last Modified:10 Oct 2017 17:26

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