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. https://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) | ||||||||||||
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Additional Information: | © 2016 American Chemical Society. | ||||||||||||
Record Number: | CaltechAUTHORS:20160913-122947066 | ||||||||||||
Persistent URL: | https://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: | 09 Mar 2020 13:19 |
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