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Published February 28, 2016 | Supplemental Material + Published
Journal Article Open

Cationic ruthenium alkylidene catalysts bearing phosphine ligands


The discovery of highly active catalysts and the success of ionic liquid immobilized systems have accelerated attention to a new class of cationic metathesis catalysts. We herein report the facile syntheses of cationic ruthenium catalysts bearing bulky phosphine ligands. Simple ligand exchange using silver(I) salts of non-coordinating or weakly coordinating anions provided either PPh3 or chelating Ph2P(CH2)nPPh2 (n = 2 or 3) ligated cationic catalysts. The structures of these newly reported catalysts feature unique geometries caused by ligation of the bulky phosphine ligands. Their activities and selectivities in standard metathesis reactions were also investigated. These cationic ruthenium alkylidene catalysts reported here showed moderate activity and very similar stereoselectivity when compared to the second generation ruthenium dichloride catalyst in ring-closing metathesis, cross metathesis, and ring-opening metathesis polymerization assays.

Additional Information

© 2016 The Royal Society of Chemistry. Received 16th November 2015, Accepted 19th January 2016. First published online 28 Jan 2016. We thank Dr M. B. Herbert for helpful discussions and suggestions for this work, Materia, Inc. for the generous donation of catalysts and Dr M. W. Day and Mr L. M. Henling for X-ray crystallography. The Bruker KAPPA APEXII X-ray diffractometer was purchased via an NSF CRIF:MU award to the California Institute of Technology, CHE-0639094. This work was financially supported by NIH (NIH 5R01GM031332), NSF (CHE-0410425 and CHE-0809418) and Mitsui Chemicals, Inc.

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Published - c5dt04506a.pdf

Supplemental Material - c5dt04506a1.pdf

Supplemental Material - c5dt04506a2.cif


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