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Acyclic diene metathesis

About: Acyclic diene metathesis is a research topic. Over the lifetime, 1903 publications have been published within this topic receiving 81665 citations.


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Journal ArticleDOI
17 Feb 1989-Science
TL;DR: The recent development of living coordinative polymerization systems has led to the preparation of a number of new, interesting materials, including block copolymers, conducting polymers or precursors, and ionophoric polymeric substrates.
Abstract: Mechanistic and synthetic studies in organometallic chemistry have provided considerable insight into olefin metathesis and Ziegler-Natta polymerization. New homogeneous olefin metathesis catalysts based on high oxidation state transition metals have opened new opportunities in polymer synthesis by providing unprecedented control in ring-opening polymerization of cyclic alkenes. The recent development of living coordinative polymerization systems has led to the preparation of a number of new, interesting materials, including block copolymers, conducting polymers or precursors, and ionophoric polymeric substrates.

401 citations

Journal ArticleDOI
TL;DR: A detailed mechanistic study of phosphine exchange and initiation kinetics in alkylidenes 1 and 2 is reported, providing new and surprising evidence concerning the origin of the large activity differences between these two catalysts.
Abstract: Over the past two decades, olefin metathesis has emerged as a mild and efficient method for the formation of carbon−carbon double bonds. In particular, (PCy_3)_2(Cl)_2RuCHPh (1)^2 has found extensive use in organic and polymer chemistry due to its high reactivity with olefins in the presence of a diverse array of functional groups. Recently, a new family of ruthenium-based olefin metathesis catalysts have been prepared by the substitution of a single PCy_3 ligand of 1 with an N-heterocyclic carbene. These new alkylidenes, particularly [Figure 1], exhibit dramatically increased activity over the parent system in ring-opening metathesis polymerization, ring-closing metathesis,4a and cross metathesis reactions. The mechanism of olefin metathesis reactions catalyzed by 1 has received intense investigation in our group and others and early studies established that phosphine dissociation is a crucial step along the reaction coordinate. As such, it has been suggested that the high activity of 2 and its analogues is due to their increased ability to promote this critical phosphine dissociation step. We report herein a detailed mechanistic study of phosphine exchange and initiation kinetics in alkylidenes 1 and 2. This study provides new and surprising evidence concerning the origin of the large activity differences between these two catalysts.

389 citations


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Performance
Metrics
No. of papers in the topic in previous years
YearPapers
20238
202221
202116
202014
201918
201815