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Scientists develop recyclable catalyst for solvent-free reactions



Morris Bullock (left) and Vladimir Dioumaev

Full size image available through contact

August 25, 2003—Chemists at the Office of Science's Brookhaven National Laboratory have developed a catalyst that achieves complete conversion of reactants to products and can easily be recovered and reused with no waste. The catalyst, described in the July 31, 2003, issue of Nature, eliminates the need for using solvents in an important step in the synthesis of many organic compounds, such as pharmaceutical agents and agricultural products.

Such a complete transformation of reactants to products without the need for additional separation steps is particularly attractive in the manufacture of pharmaceuticals, which must be pure and free from residual metal catalysts. But it should be of interest to all in industry who seek to reduce waste and the cost of manufacturing processes.

"Avoiding the use of solvents is an important way to prevent waste in chemical manufacturing processes," said Brookhaven chemist Morris Bullock, who led the research. This new catalyst, developed by Vladimir Dioumaev, a post-doc in Bullock's lab, achieves that goal in two ways: First, as a homogeneous catalyst, it dissolves in the reactants. That eliminates the need for a solvent to mix the reagents to get the reaction going. Second, it precipitates as a solid at the end of the reaction, so no solvents or additional steps are required to separate the catalyst from the products.

"It separates itself. You can simply pour the products into another container and use the catalyst again," Dioumaev said.

The catalyst is soluble in one of the reagents and remains soluble when the other reagent is added. As the reaction goes on, and the product builds up, the catalyst precipitates from the mixture as oil. This oil—liquid clathrate—remains to be an active catalyst, as the reagents are able to penetrate into it. When all the reagents are converted into products, the oily catalyst turns into a sticky solid, which can be easily separated and recycled.



The catalyst is soluble in one of the reagents and remains soluble when the other reagent is added. As the reaction goes on, and the product builds up, the catalyst precipitates from the mixture as oil. This oil—liquid clathrate—remains to be an active catalyst, as the reagents are able to penetrate into it. When all the reagents are converted into products, the oily catalyst turns into a sticky solid, which can be easily separated and recycled.

Full size image available through contact

"The concept is simple, but striking the right balance between maintaining catalyst solubility throughout the reaction and precipitation at the end is a diabolical problem," Bullock said. Homogeneous catalysts usually remain dissolved at the end of the reaction, presenting a problem in recovery of the catalyst. But a catalyst that precipitates before the reaction is over would lead to incomplete conversion of the reactants. The Brookhaven team was trying to develop a catalyst that would retain some solubility in the liquid phase until all the reactants were used up, but which would then precipitate to facilitate recovery and recycling of the catalyst.

To explore the concept, the scientists investigated a variety of catalysts designed to react ketones, a class of organic molecules, with organic silicon compounds. These reactions, called hydrosilylation reactions, can be used in the manufacture of drugs, pesticides, and other organic compounds. The products of such reactions are also used in the preparation of ceramic materials.

The catalysts they experimented with had been found in their earlier work to dissolve in ketones but form oily precipitates, known as liquid clathrates, from many other solvents. Such an oily phase, they thought, might be ideal for maintaining the ability to catalyze the reaction to completion, because the oil would allow access to the liquid reactants rather than settling out as a solid precipitate would. By experimentally altering the structure of the catalyst, the scientists arrived at a formulation containing the metal tungsten that accomplished their goal.

At first, the catalyst mixes readily with the reactants. Then, as the reaction progresses to near completion, the catalyst begins to precipitate, but remains suspended as an oily liquid clathrate, clearly visible in the tube where the reaction is taking place.

"The reagents can penetrate the oil to keep reacting until all the reactants are used up," Dioumaev said. When that happens, the no-longer-soluble catalyst precipitates out as a solid, which settles to the bottom of the test tube. Analysis revealed that there was essentially no catalyst remaining in the liquid products.

The Brookhaven scientists plan to continue their research to see if this general method of catalyst self-separation using liquid clathrate catalysts can be applied to other reactions. This research often requires knowledge of the molecular structure of the catalyst, and the tungsten catalyst used in this research was deciphered at the National Synchrotron Light Source at Brookhaven Lab. A paper on the structural determination was recently published in Chemical Communications.

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—by Karen McNulty Walsh

Related Web Links

"A Recyclable Catalyst that Precipitates at the End of the Reaction." Dioumaev, VK, and RM Bullock. July 31, 2003. Nature 424(6948):530-531 (subscription may be required)

"An N-Heterocyclic Carbene as a Bidentate Hemilabile Ligand in W and Mo Hydrogenation Catalysts: A Synchrotron X-ray Diffraction and Density Functional Theory Study." Dioumaev, VK, and DJ Szalda, J Hanson, JA Franz, and RM Bullock. 2003. Chemical Communications 14:1670-1671 (subscription may be required)

Brookhaven Lab and DuPont Develop New Catalysts to Convert Renewable Feedstocks to Useful Industrial Materials

Funding: This research was funded by the Basic Energy Science program's Division of Chemical Sciences within the DOE's Office of Science.

Brookhaven National Laboratory conducts research in the physical, biomedical, and environmental sciences, as well as in energy technologies. Brookhaven also builds and operates major facilities available to university, industrial, and government scientists. The Laboratory is managed by Brookhaven Science Associates, a limited liability company founded by Stony Brook University and Battelle, a nonprofit applied science and technology organization.

Author: Karen McNulty Walsh, a Senior Public Affairs Representative at Brookhaven National Laboratory since September 1999, has an MA in science journalism from New York University and a BA in biology from Vassar College. She was previously the editor of Science World, a science magazine for middle-school children, and Zillions, a kids' version of Consumer Reports. For more science news, see Brookhaven Laboratory News.

 

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