Science Watch® - Tracking Trends and Performance in Basic Research
March/April 2006


Gold-Plated Titanium and Palladium Catalysts by John Emsley
WHAT'S HOT IN CHEMISTRY
Rank      Paper Citations This Period (Sep-Oct 05) Rank Last Period (Jul-Aug 05)
1 L.C. Storoni, A.J. McCoy, R.J. Read, "Likelihood-enhanced fast rotation functions," Acta Cryst. D, 60: 432-8, March 2004. [U. Cambridge, U.K.] *778CQ 21 9
2 H.K. Chae, et al., "A route to high surface area, porosity and inclusion of large molecules in crystals," Nature, 427(6974): 523-7, 5 February 2004. [U. Michigan, Ann Arbor; Arizona St. U., Tempe] *770KM 20 5
3 L.R. Hirsch, et al., "Nanoshell-mediated near-infrared thermal therapy of tumors under magnetic resonance guidance," Proc. Natl. Acad. Sci. USA, 100(23): 13549-54, 11 November 2003. [Rice U., Houston, TX; U. Texas, M.D. Anderson Cancer Ctr., Houston] *743LR 20
4 X.Y. Kong, et al., "Single-crystal nanorings formed by epitaxial self-coiling of polar nanobelts," Science, 303(5662): 1348-51, 27 February 2004. [Georgia Inst. Tech., Atlanta] *778JN 19 2
5 Y.F. Shen, et al., "Ultra-high-effciency strong cation exchange LC/RPLC/MS/MS for high dynamic range characterization of the human plasma proteome," Analyt. Chem., 76(4): 1134-44, 15 February 2004. [Pacific NW Lab., Richland, WA; Stanford U. Sch. Med., CA; Harvard Med. Sch., Boston, MA] *776QC 19
6 M.S. Chen, D.W. Goodman, "The structure of catalytically active gold on titania," Science, 306(5694): 252-5, 8 October 2004. [Texas A&M U., College Station] *861MC 18
7 S.D. Walker, et al., "A rationally designed universal catalyst for Suzuki-Miyaura coupling processes," Angew. Chem. Int. Ed., 43: 1750-7, 2004. [MIT, Cambridge, MA] *809TG 15
8 S. Helveg, et al., "Atomic-scale imaging of carbon nanofibre growth," Nature, 427(6973): 426-9, 29 January 2004. [Tech. U. Denmark, Lyngby] *767UF 14
9 D.N. Dybtsev, et al., "Microporous manganese formate: a simple metal-organic porous material with high framework stability and highly selective gas sorption properties," J. Am. Chem. Soc., 126(1): 32-3, 14 January 2004. [Pohang U., Korea] *761ZM 14
10 J. Huang, R.B. Kaner, "A general chemical route to polyaniline nanofibers," J. Am. Chem. Soc., 126(3): 851-5, 28 January 2004. [U. Calif., Los Angeles] *756YH 14
 SOURCE: Thomson Scientific Hot Papers DatabaseRead  the Legend.

Two papers in the current Hot Ten deal with metal catalysts; paper #6 is about gold and paper #7 about palladium.

Paper #6 is the work of Wayne Goodman and Mingshu Chen of Texas A&M University and describes the remarkable catalytic power of gold atoms supported on titanium dioxide (TiO2). An earlier and much-cited paper of Goodman’s (M. Valden, et al., Science, 281[5383]: 1647-50, 1998) reported on the excellent catalytic properties of gold clusters on TiO2, and the current work is a major step forward in understanding them. Moreover, it is the first example of complete "wetting" of an oxide surface by gold atoms and proves that such an ultra-thin gold film can act as a catalyst for CO oxidation and that gold nanoparticles as such are not essential for catalytic activity, as originally speculated.

The new catalyst was made by building a layer of TiO2 on a molybdenum substrate and then depositing a layer of gold, only one or two atoms thick, on top. This was annealed at 900 K to form a well-ordered layer of gold atoms which was shown to be bonded directly to titanium atoms and not to oxygens. Goodman and Chen then tested the catalytic efficiency of the gold films by their abilities to oxidize CO at room temperature, which was up to 45 times better than the most reactive gold/TiO2 surface previously reported.

Currently Goodman’s group is studying these gold layers and related materials as potential catalysts. They are also synthesizing functional oxide supports for stabilizing thin gold films, and in related work they have addressed the promotional effect of the gold in palladium-gold catalysts for the synthesis of vinyl acetate (see M.S. Chen, et al., Science, 310[5746]: 291-3, 2005). Speaking to Science Watch, Goodman commented: "We are hopeful and very optimistic that the methodologies used to synthesize highly active model gold catalysts can be utilized to prepare vastly superior high-surface-area catalysts for a variety of industrial applications." A golden age of catalysis may well be dawning.

Paper #7 also involves palladium as a catalyst, in this case for the Suzuki-Miyaura coupling reaction, in which two benzene rings join together by the reaction of a boronic acid group on one molecule with a chlorine atom on the other, the result being a biaryl. The work was done by Stephen Buchwald’s group at MIT, and what is particularly striking is the way the catalyst was designed rather than being discovered by accident or by testing possible candidates.

Making a hindered biaryl is what the Suzuki-Miyaura process is all about. If the benzene-ring carbons adjacent to the boronic acid group and the chlorine carry other substituents, and especially bulky substituents, then making the biaryl becomes somewhat problematical, as the region of space surrounding the bond to be formed is highly congested. Palladium complexes can, however, catalyze the process, and in paper #7 a new "universal" catalyst is reported.

The new catalyst is a biaryl phosphorus compound which can complete a Suzuki-Miyaura reaction in a couple of hours, with yields in excess of 90%, catalyst concentrations of 0.2% Pd or less, and at room temperature. Even with only 0.02% of catalyst present in the reaction it is still possible to obtain comparable yields, although these require heat and take much longer. In one reaction, and using only 30 ppm (0.003%) of catalyst, Buchwald was able to calculate that each Pd participated in 31,000 individual reactions. He was even able to report that at a mere 10 ppm there was still significant catalytic activity.

The versatility of the new catalyst is such that even the most congested biaryls can be produced with all four carbons adjacent to the biaryl bond having groups attached, and yields were still in excess of an unbelievable 80%. The new catalyst also works for the coupling of heteroaryl compounds and again in yields above 95%. Since paper #7, Buchwald has published further research into the Suzuki-Miyaura coupling reaction, in one case looking at trifluoroborate as the reacting group (see T.E. Barder, S.L. Buchwald, Organic Letters, 6[17]: 2649-52, 2004) and, more recently, reporting new catalysts with modified ligand structures (see T.E. Barder, et al., J. Am. Chem. Soc., 127[13]: 4685-96, 2005).end

Dr. John Emsley is based at the Department of Chemistry, Cambridge University, U.K.

View the top 10 scientists and/or top 3 Hot Papers in Chemistry.
Science Watch®, March/April 2006, Vol. 17, No. 2
Citing URL: http://www.sciencewatch.com/march-april2006/sw_march-april2006_page7.htm

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