In recent years, the olefin metathesis reaction has attracted widespread attention as a versatile carbon−carbon bond-forming method. Many new applications have become possible because of major advances in catalyst design. State-of-the-art ruthenium catalysts are not only highly active but also compatible with most functional groups and easy to use. This Account traces the ideas and discoveries that were instrumental in the development of these catalysts, with particular emphasis on (PCy3)2Cl2RuCHPh and its derivatives. The discussion includes an analysis of trends in catalyst activity, a description of catalysts coordinated with N-heterocyclic carbene ligands, and an overview of ongoing work to improve the activity, stability, and selectivity of this family of L2X2RuCHR complexes.

http://web4.uwindsor.ca/users/j/jlichaa/reference.nsf/0/10ff8b04ff3a317885256d88005720f6/$FILE/acr-2001-34-18-metath-grubbs.pdf

The Development of L2X2RuCHR Olefin Metathesis Catalysts: An Organometallic Success Story

The fascinating story of olefin (or alkene) metathesis (eq
1) began almost five decades ago, when Anderson and
Merckling reported the first carbon-carbon double-bond
rearrangement reaction in the titanium-catalyzed polymerization of norbornene. Nine years later, Banks and Bailey reported “a new disproportionation reaction . . . in which olefins are converted to homologues of shorter and longer carbon chains...”. In 1967, Calderon and co-workers named this metal-catalyzed redistribution of carbon-carbon double bonds olefin metathesis, from the Greek word “μeτάθeση”, which means change of position. These contributions have since served as the foundation for an amazing research field, and olefin metathesis currently represents a powerful transformation in chemical synthesis, attracting a vast amount of interest both in industry and academia.

https://core.ac.uk/download/pdf/4884240.pdf

Ruthenium-based heterocyclic carbene-coordinated olefin metathesis catalysts.

Living ring-opening metathesis polymerization

This is a story of our exploration of the olefin-metathesis reaction, a reaction that has been the major emphasis of my independent research. As with all stories of scientific discovery, there are three components: the discoveries, the resulting applications, and, perhaps the most important of all, the people involved. Starting from observations made from seemingly unrelated work, our investigations into the fundamental chemistry of this transformation have been an exciting journey, with major advances often resulting from complete surprises, mistakes, and simple intuition. Ultimately, these efforts have contributed to olefin metathesis becoming the indispensable synthetic tool that it is today.

Olefin-metathesis catalysts for the preparation of molecules and materials (Nobel Lecture)

Homogeneous Metathesis Polymerization by Well-Defined Group VI and Group VIII Transition-Metal Alkylidenes: Fundamentals and Applications in the Preparation of Advanced Materials.

Olefin metathesis. I. Acyclic vinylenic hydrocarbons

Olefin metathesis - A novel reaction for skeletal transformations of unsaturated hydrocarbons

Equilibrium ring-opening polymerization theory has been extended to cycloolefin polymerizations. Previous work had established the reversible nature of the olefin metathesis reaction, the basic process whereby cycloolefins undergo ring-opening. The present work confirms the reversible character of cycloolefin polymerization for the cases of cyclopentene and bicyclo[4.3.0]nona-3.7-diene polymerization. Equilibrium conversion data for cyclopentene polymerizations have provided estimates of the enthalpy (−4.4 kcal/mole) and entropy (−14.9 cal/mole·deg) of polymerization. In addition, some factors governing the polymerizability of mono- and multicyclic monomers are discussed.



Die Theorie der ringoffnenden Gleichgewichtspolymerisation wurde auf die Polymerisation von Cycloolefinen ausgedehnt. In fruheren Arbeiten wurde die reversible Natur der Olefin-Metathese aufgezeigt, der Grundprozes, nach dem Cycloolefine einer Ringoffnung unterliegen. Die vorliegende Arbeit bestatigt den reversiblen Charakter der Cycloolefin-polymerisation fur Cyclopenten und Bicyclo-[4.3.0]-nona-3.7-dien. Die Daten des Reaktionsgleichgewichts der Polymerisation von Cyclopenten lassen eine Abschatzung der Enthalpie der Polymerisation (−4,4 kcal/Mol) und der Polymerisationsentropie (−14,9 cal/Mol·Grad) zu. Auserdem werden einige Faktoren diskutiert, die die Polymerisierbarkeit von mono- und multicyclischen Monomeren beeinflussen.

Equilibrium ring‐opening polymerization of mono‐ and multicyclic unsaturated monomers

The ring-opening polymerizations of cyclooctene, cyclododecene, 1,5-cyclooctadiene, 1,5,9-cyclododecatriene, 3-methylcyclooctene, and 3-phenylcyclooctene have been carried out by using a two-component catalyst system composed of ethylaluminum dichloride and tungsten hexachloride. NMR and infrared analyses of the respective polymers indicate structures which are consistent with a ring-cleavage mode of propagation. No evidence for double-bond shifts or transannular reactions during the polymerizations of 1,5-cyclooctadiene, 1,5,9-cyclododecatriene, 3-methylcyclooctene, and 3-phenylcyclooctene was found. The polymerizability of substituted, unsaturated, mediumsized alicyclic monomers suggests a convenient method for synthesis of certain perfectly alternating terpolymers. Since polymerizations occurred rapidly with little evolution of heat, it was concluded that entropy is a substantial contributor to the free energy of the ring-opening polymerization of medium-sized, unsaturated alicyclic monomers.

Ring-opening polymerization of unsaturated alicyclic compounds

By utilizing the vapor phase polymerisation techniques of the present invention, numerous distinct and highly beneficial advantages are realized. For instance, cis-1,4-polybutadiene and high cis-1,4-polybutadiene rubber having a consistent and controllable molecular weight can be easily and practically prepared without utilizing a solvent. The supported catalyst is mixed prior to its introduction into the reaction zone. The supported, preformed catalyst system is introduced into the reaction zone (11) by feeding the catalyst into the reactor via catalyst feed line (27) at point (28) which is in the upper portion of the reaction zone.

Nissim Calderon

Papers

Olefin metathesis. I. Acyclic vinylenic hydrocarbons

Olefin metathesis - A novel reaction for skeletal transformations of unsaturated hydrocarbons

Equilibrium ring‐opening polymerization of mono‐ and multicyclic unsaturated monomers

Ring-opening polymerization of unsaturated alicyclic compounds

Vapor phase synthesis of rubbery polymers