Mechanism and Activity of Ruthenium Olefin Metathesis Catalysts

This report details the effects of ligand variation on the mechanism and activity of ruthenium-based olefin metathesis catalysts. A series of ruthenium complexes of the general formula L(PR3)(X)2RuCHR1 have been prepared, and the influence of the substituents L, X, R, and R1 on the rates of phosphi...

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Veröffentlicht in:Journal of the American Chemical Society 2001-07, Vol.123 (27), p.6543-6554
Hauptverfasser: Sanford, Melanie S, Love, Jennifer A, Grubbs, Robert H
Format: Artikel
Sprache:eng
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Zusammenfassung:This report details the effects of ligand variation on the mechanism and activity of ruthenium-based olefin metathesis catalysts. A series of ruthenium complexes of the general formula L(PR3)(X)2RuCHR1 have been prepared, and the influence of the substituents L, X, R, and R1 on the rates of phosphine dissociation and initiation as well as overall activity for olefin metathesis reactions was examined. In all cases, initiation proceeds by dissociative substitution of a phosphine ligand (PR3) with an olefinic substrate. All of the ligands L, X, R, and R1 have a significant impact on initiation rates and on catalyst activity. The origins of the observed substituent effects as well as the implications of these studies for the design and implementation of new olefin metathesis catalysts and substrates are discussed in detail.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja010624k