Origins of Initiation Rate Differences in Ruthenium Olefin Metathesis Catalysts Containing Chelating Benzylidenes

A series of second-generation ruthenium olefin metathesis catalysts was investigated using a combination of reaction kinetics, X-ray crystallography, NMR spectroscopy, and DFT calculations in order to determine the relationship between the structure of the chelating o-alkoxybenzylidene and the obser...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2015-05, Vol.137 (17), p.5782-5792
Main Authors: Engle, Keary M., Lu, Gang, Luo, Shao-Xiong Lennon, Henling, Lawrence M., Takase, Michael K., Liu, Peng, Houk, K. N., Grubbs, Robert H.
Format: Article
Language:English
Subjects:
Alkenes - chemistry
Benzylidene Compounds - chemistry
Catalysis
Chelating Agents - chemistry
Crystallography, X-Ray
Magnetic Resonance Spectroscopy
Models, Molecular
Molecular Structure
Organometallic Compounds - chemical synthesis
Organometallic Compounds - chemistry
Quantum Theory
Ruthenium - chemistry
Thermodynamics
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Summary:A series of second-generation ruthenium olefin metathesis catalysts was investigated using a combination of reaction kinetics, X-ray crystallography, NMR spectroscopy, and DFT calculations in order to determine the relationship between the structure of the chelating o-alkoxybenzylidene and the observed initiation rate. Included in this series were previously reported catalysts containing a variety of benzylidene modifications as well as four new catalysts containing cyclopropoxy, neopentyloxy, 1-adamantyloxy, and 2-adamantyloxy groups. The initiation rates of this series of catalysts were determined using a UV/vis assay. All four new catalysts were observed to be faster-initiating than the corresponding isopropoxy control, and the 2-adamantyloxy catalyst was found to be among the fastest-initiating Hoveyda-type catalysts reported to date. Analysis of the X-ray crystal structures and computed energy-minimized structures of these catalysts revealed no correlation between the 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 the rationalization and prediction of catalyst initiation through the calculation of a single thermodynamic parameter in which no assumptions about the mechanism of the initiation step are made.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.5b01144