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An Initiation Kinetics Prediction Model Enables Rational Design of Ruthenium Olefin Metathesis Catalysts Bearing Modified Chelating Benzylidenes

Luo, Shao-Xiong and Engle, Keary M. and Dong, Xiaofei and Hejl, Andrew and Takase, Michael K. and Henling, Lawrence M. and Liu, Peng and Houk, K. N. and Grubbs, Robert H. (2018) An Initiation Kinetics Prediction Model Enables Rational Design of Ruthenium Olefin Metathesis Catalysts Bearing Modified Chelating Benzylidenes. ACS Catalysis, 8 (5). pp. 4600-4611. ISSN 2155-5435. PMCID PMC7289044.

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Rational design of second-generation ruthenium olefin metathesis catalysts with desired initiation rates can be enabled by a computational model that is dependent on a single thermodynamic parameter. Using a computational model with no assumption about the specific initiation mechanism, the initiation kinetics of a spectrum of second-generation ruthenium olefin metathesis catalysts bearing modified chelating ortho-alkoxy benzylidenes were predicted in this work. Experimental tests of the validity of the computational model were achieved by the synthesis of a series of ruthenium olefin metathesis catalysts and investigation of initiation rates by ultraviolet–visible light (UV-vis) kinetics, nuclear magnetic resonance (NMR) spectroscopy, and structural characterization by X-ray crystallography. Included in this series of catalysts were 13 catalysts bearing alkoxy groups with varied steric bulk on the chelating benzylidene, ranging from ethoxy to dicyclohexylmethoxy groups. The experimentally observed initiation kinetics of the synthesized catalysts were in good accordance with computational predictions. Notably, the fast initiation rate of the dicyclohexylmethoxy catalyst was successfully predicted by the model, and this complex is believed to be among the fastest initiating Hoveyda–Grubbs-type catalysts reported to date. The compatibility of the predictive model with other catalyst families, including those bearing alternative N-heterocyclic carbene (NHC) ligands or disubstituted alkoxy benzylidenes, was also examined.

Item Type:Article
Related URLs:
URLURL TypeDescription Information CentralArticle
Luo, Shao-Xiong0000-0001-5308-4576
Engle, Keary M.0000-0003-2767-6556
Takase, Michael K.0000-0001-8365-3645
Liu, Peng0000-0002-8188-632X
Houk, K. N.0000-0002-8387-5261
Grubbs, Robert H.0000-0002-0057-7817
Additional Information:© 2018 American Chemical Society. Received: March 2, 2018; Revised: March 30, 2018; Published: April 10, 2018. We acknowledge Dr. Bruce S. Brunschwig for assistance with the UV-vis kinetics experiments, which were carried out at the Molecular Materials Research Center of the Beckman Institute at Caltech. The research described in this manuscript was supported financially by the ONR (Award No. N00014-14-1-0650) and the NIH NIGMS (No. F32GM108145, postdoctoral fellowship to K.M.E.). The Bruker KAPPA APEXII X-ray diffractometer was purchased via an NSF CRIF:MU award to the California Institute of Technology (No. CHE-0639094). We thank Materia, Inc. for the generous donation of catalysts 2–5, 33, 36, and 39. Calculations were performed on supercomputers from the DoD HPCMP Open Research Systems and the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by the NSF. Dr. Tzu-Pin Lin, Dr. Crystal K. Chu and Dr. Timothy P. Montgomery are acknowledged for helpful discussions and assistance with NMR experiments. The authors declare no competing financial interest.
Funding AgencyGrant Number
Office of Naval Research (ONR)N00014-12-1-0596
NIH Postdoctoral FellowshipF32GM108145
Subject Keywords:olefin metathesis, Grubbs–Hoveyda typed complexes, N-heterocyclic carbenes, initiation kinetics, prediction model
Issue or Number:5
PubMed Central ID:PMC7289044
Record Number:CaltechAUTHORS:20180411-114458529
Persistent URL:
Official Citation:An Initiation Kinetics Prediction Model Enables Rational Design of Ruthenium Olefin Metathesis Catalysts Bearing Modified Chelating Benzylidenes. Shao-Xiong Luo, Keary M. Engle, Xiaofei Dong, Andrew Hejl, Michael K. Takase, Lawrence M. Henling, Peng Liu, K. N. Houk, and Robert H. Grubbs. ACS Catalysis 2018 8 (5), 4600-4611. DOI: 10.1021/acscatal.8b00843
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:85751
Deposited By: George Porter
Deposited On:11 Apr 2018 20:46
Last Modified:15 Jun 2020 16:05

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