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Book your free demo and find out what else Mya 4 from Radleys can do. The discoveries made by this year's Nobel laureates have had a great impact on new drug developments, polymeric materials and industrial syntheses. Karen Harries-Rees reports. Metathesis, which literally means to change places, provides a way of breaking and remaking carbon-carbon double bonds.
In olefin alkene metathesis, carbon-carbon double bonds in alkenes are broken and reformed, and in the process substituent groups are swapped. Catalysed metathesis reactions give shorter synthesis routes, yielding more product, resulting in cleaner and more environmentally friendly production.
It has great commercial potential in the pharmaceuticals industry, the biotechnology industry and in food production. New metathesis catalysts are also widely applicable in polymer synthesis, with recent research focusing on creating polymers with specific characteristics.
Other applications include synthesising insect pheromones, herbicides, and additives for polymers and fuels. Catalysed metathesis was first discovered in the s by industrial researchers, although the mechanisms were not understood at the time. A number of patents described the catalysation of olefin polymerisation, including one in by Herbert Eleuterio at DuPont in the US which described the formation of unsaturated polymers.
Earlier attempts to polymerise ethene to polyethene had only produced saturated polymers. Catalysed metathesis was first discovered in the s in industry but the mechanisms were not understood. In the same year another patent showed that propene could be converted into butene and ethene when treated with a mixture of triisobutyl aluminium and molybdenum oxide on aluminium oxide. Calderon showed that the same type of reaction, which he termed olefin metathesis, took place in both processes.
In the metathesis of an alkene, a metal carbene later termed metal alkylide acts as a catalyst for the exchange of alkylidenes between two different alkenes and the result is two entirely new alkenes. In this mechanism, in the first stage a metal methylene metal alkylidene reacts with the alkene, forming a metallocyclobutane intermediate.
In the next step, two of the single bonds are broken and a new alkene ethene and a new metal alkylidene is obtained. In the third step, this new metal alkylidene unites with one of the original alkenes to form a new metallocyclobutane. In the last stage, this intermediate molecule is broken apart, giving a metathesis product and reforming the metal methylene catalyst.
Olefin metathesis - Wikipedia
The result is that the two molecules have exchanged alkylidene groups with each other; they have undergone metathesis. But that happens to lots of others in science, that it is while you are resting that great ideas come to you. Chauvin and co-workers also had experimental support for the mechanism that could not be explained by other proposed mechanisms. It has also received strong experimental support from Schrock and Grubbs, among others, and is now generally accepted.
Chemists saw great potential in metathesis.
But its application in organic chemistry was difficult because available catalysts were sensitive to air and moisture, created side reactions and were relatively short-lived. Stable and well-defined catalysts with reactivity that could be adjusted to suit the purpose were needed. Schrock joined DuPont in , attracted by its vibrant basic research. The company allowed researchers to choose their own research, provided it had some relationship to one of its interests which, at the time, included polyethylene, polypropylene and polyolefin research.
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However, what he isolated instead was the first stable metal-alkylidene complex. That compound led me to these catalysts. Schrock tried other tantalum-alkylidene complexes, including the first methylene complex. He also found that metallocyclobutanes were formed. But none of the complexes catalysed olefin metathesis. This worked where other complexes had failed because it had alkoxide ligands. He gradually developed an understanding of which metals could be used. Molybdenum and tungsten soon appeared to be the most suitable.
Schrock and his group worked to find alkylidene complexes of these metals. The search eventually produced a family of molybdenum- and tungsten-alkylidene complexes, and the most efficient were reported in One is commercially available and these compounds are now the most active of the alkene metathesis catalysts. But these catalysts were unstable and sensitive to oxygen and water. Grubbs recognised this and with his co-workers found that ruthenium trichloride polymerised olefins even in water. Ruthenium chloride had already been used by Giulio Natta as a catalyst for polymerisation of cyclobutene by ring opening.
His most recent focus is on the synthesis and applications of new olefin metathesis catalysts for Z selective olefin metathesis reactions. Schrock has been an Alfred P.
Chauvin and R. He has received honorary degrees from the universities of Zaragoza, Rennes, St. He was Associate Editor of Organometallics for eight years, and has published over research papers. Skip to main content. Home Research People Past Ph. About Richard Schrock Richard R.