Discovery of olefin metathesis

In Chauvin proposed a four-membered metallacycle intermediate to explain the statistical distribution of products found in certain metathesis reactions. Managerial positions he held were related to polymer intermediates, explosives, atomic energy and long-range research.

In any of the pairwise mechanisms with olefin pairing as rate-determining step this compound, a secondary reaction product of C12 with C6, would form well after formation of the two primary reaction products C12 and C When we submitted the paper, we thought we were proposing a new mechanism for olefin metathesis that involved metal carbenes.

During those five years, he showed that the tantalum compounds form metallacyclobutanes. Later, he suggested that one mode of rearrangement could lead to formation of a cyclobutane complexed to a metal carbene [Inorg. Chauvin, now Discovery of olefin metathesis, says three papers published in led him to the hypothesis.

Cross metathesis and ring-closing metathesis are driven by the entropically favored evolution of ethylene or propylenewhich can be removed from the system because they are gases. He was the guy who first pointed out how to get over the hill.

Historical overview[ edit ] "Olefin metathesis is a child of industry and, as with many catalytic processes, it was discovered by accident. This mechanism is pairwise: When the backbone double bonds of the resultant polymers are quantitatively hydrogenated, unusual functional polyethylenes are obtained.

With McGinnis and undergraduate student Samuel Hurwitz, he reported the first use of an isolable metal-carbene complex-- diphenylcarbene pentacarbonyltungsten--to initiate metathesis of unsymmetrically substituted ethylenes [J. The Grubbs group successfully polymerized the 7-oxo norbornene derivative using ruthenium trichlorideosmium trichloride as well as tungsten alkylidenes.

Evering recorded in U. For example, Mol concluded in that the available data supporting the Chauvin hypothesis did not exclude other mechanisms. Such a route to polyacetylenes was first proposed by Toshio Masuda and coworkers at Kyoto University, Japan, who showed that phenylacetylene is polymerized by tungsten hexachloride or molybdenum pentachloride [Macromolecules, 8, ].

Monomers incorporating ether, alcohol, sulfur, silane, and stannane groups have been polymerized 64— Ring-opening metathesis polymerization, or ROMP, involves an addition chain building mechanism from cyclic monomers containing a single double bond.

InHerbert S. Up to that point, researchers--including Chauvin, Grubbs, and Katz--had been initiating olefin metathesis reactions with ill-defined mixtures. He discovered that hexafluoropropylene could be co-polymerized with tetrafluoroethylene to yield amorphous fluorinated ethylene propylene co-polymers with good characteristics as films.

Herbert S. Eleuterio

On the other hand, Grubbs did not rule out the possibility of a tetramethylene intermediate. And with Acton, he showed that another carbene, methoxyphenylcarbene pentacarbonyltungsten, also initiates polymerization of cyclobutene and norbornene [Tetrahedron Lett.

Casey and Terry J. Bailey, of Phillips Petroleum, Bartlesville, Okla.

We started in the late s," he says. But the relevance of this reaction to ordinary alkenes was "an open question" at the time [Chem.

He subsequently joined the research staff at the DuPont Co. In an attempt to explain olefin metathesis, Grubbs--who by then had moved to Michigan State University, East Lansing--proposed that the redistribution of groups around the double bonds was due to a rearranging metallacyclopentane intermediate [J.The first compounds, however, were not productive in olefin metathesis; the metallacyclobutanes rearranged before they could form a new olefin.

Schrock's lab prepared and characterized many new tantalum, as well as niobium, complexes and tested them in olefin metathesis.


Herbert S. Eleuterio (born November 23, ) is an American industrial chemist noted for technical contributions to catalysis, polymerization, industrial research management, and science education.

In particular, he discovered the olefin metathesis reaction and several novel mint-body.comutions: DuPont Co., National University of Singapore.

The discovery has seen many applications since the 90s, thanks to its selectivity and its ability to make complex chemical reactions easy. Olefin metathesis entails the redistribution of alkene fragments (olefins) by the scission and regeneration of carbon-carbon double bonds.

Olefin metathesis

Olefin Metathesis Catalysis: The Beginning • Transition metal-chlorides in the presence of co-catalysts were the first to be studied that afforded C-C bond formation. Since the discovery of olefin metathesis in the mids, there has been great interest in using this versatile reaction to synthesize macromolecular materials.

Olefin metathesis is an organic reaction that entails the redistribution of fragments of alkenes (olefins) For their elucidation of the reaction mechanism and their discovery of a variety of highly active catalysts, Yves Chauvin, Robert H.

Grubbs, Organic Chemistry Portal: olefin-metathesis.

Discovery of olefin metathesis
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