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Origins of initiation rate differences in ruthenium olefin metathesis catalysts containing chelating benzylidenes

Academic Article
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Overview

authors

  • Engle, Keary M.
  • Lu, G.
  • Luo, S. X.
  • Henling, L. M.
  • Takase, M. K.
  • Liu, P.
  • Houk, K. N.
  • Grubbs, R. H.

publication date

  • May 2015

journal

  • Journal of the American Chemical Society  Journal

abstract

  • 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.

subject areas

  • Alkenes
  • Benzylidene Compounds
  • Catalysis
  • Chelating Agents
  • Crystallography, X-Ray
  • Magnetic Resonance Spectroscopy
  • Models, Molecular
  • Molecular Structure
  • Organometallic Compounds
  • Quantum Theory
  • Ruthenium
  • Thermodynamics
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Identity

International Standard Serial Number (ISSN)

  • 0002-7863

Digital Object Identifier (DOI)

  • 10.1021/jacs.5b01144

PubMed ID

  • 25897653
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Additional Document Info

start page

  • 5782

end page

  • 5792

volume

  • 137

issue

  • 17

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