Abstract

Surface Science Meets Homogeneous Catalysis

When chemisorbed upon certain surfaces, the reactivity of many types of organometallic molecules is dramatically enhanced in ways that historically have been poorly understood.

High activities for a variety of catalytic reactions are illustrative consequences of this altered reactivity. This lecture focuses on the intricate non-covalent and covalent multi-center interactions that modulate these catalytic processes, focusing primarily on polymerization and hydrogenation/dehydrogenation processes. Specific interrelated topics include:

• Catalytic chemistry of mononuclear and multinuclear d⁰ catalysts anchored on/activated by surfaces versus those in homogeneous solution

• Catalytic chemistry and cooperativity effects in multinuclear groups 4 and 6 catalysts in homogeneous solution

• Definitive structural characterization of these catalysts on “super-acidic” oxide surfaces, and the broad scope of their catalytic properties

• Unusual catalytic chemistry of group 6 dioxo complexes adsorbed on activated carbon surfaces. It will be seen that the information obtained from these studies leads to design rules for next-generation homogeneous and supported catalysts, and for novel and useful polymerization and hydrogenation/dehydrogenation processes, such as the catalytic detoxification of gasoline, stereoselective aromatics hydrogenation, biofeedstock transesterification, and bio-alcohol dehydrogenation.

References

1. Stalzer, M.M.; Nicholas, C.P.; Bhattacharyya, A.; Motta, A.; Delferro, M..; Marks, T.J.; Angew. Chem. Int. Ed. 2016, 55, 5263–5267.

2. Gu, W.; Stalzer, M.M.; Nicholas, C.P.; Bhattacharyya, A.; Motta, A.; Gallagher, J.R.; Zhang, G.; Miller, J.T.; Kobayashi, T.; Pruski, M.; Delferro, M.; Marks, T.J J. Am. Chem. Soc. 2015, 137, 6770–6780.

3. Stalzer, M.M.; Delferro, M.; Marks, T.J.; Catalysis Letters, 2015, 145, 3-14.

4. Williams, L.A.; Guo, N.; Motta, A.; Delferro, M.; Fragala, I.L.; Miller, J.T.; Marks, T.J. Proc. Nat. Acad. Sci., 2013, 110, 413-418.

5. Liu, S.; Invergo, A.M.; McInnis, J.P.; Mouat, A.R.; Motta, A.; Lohr, T.L.; Delferro, M.; Marks, T.J.; Organometallics 2017, in press. DOI:org/10.1021/acs.organomet.7b00641.

6. McInnis, J.P.; Delferro, M.; Marks, T.J.; Accts. Chem. Res., 2014, 47, 2545–2557.

7. Liu, S.; Li, J.; Jurca, T.; Lohr, T.L.; Stair, P.C.; Marks, T.J. Catalysis Science & Technology, 2017, 7, 2165 – 2169.

8. Mouat, A.R.; Lohr, T.L.; Wegener, E.C.; Miller, J.T.; Delferro, M.; Stair, P.C.; Marks, T.J.; ACS Catalysis, 2016, 6,6762–6769.

9. Lohr, T.L.; Mouat, A.R.; Schweitzer, N.M.; Stair, P.C.; Delferro, M.; Marks, T.J.; 2017, Energy Environ. Sci., 2017, 10, 1558-1562.

Biography

Tobin Marks is Vladimir Ipatieff Professor of Catalytic Chemistry, Professor of Materials Science and Engineering, Professor of Chemical and Biological Engineering, and Professor of Applied Physics at Northwestern University.

His recognitions include the U.S. National Medal of Science, the Spanish Principe de Asturias Prize, the MRS Von Hippel Award, the Dreyfus Prize in the Chemical Sciences, the National Academy of Sciences Award in Chemical Sciences, and the American Chemical Society Priestley Medal. He is a member of the U.S., German, and Indian National Academies of Sciences, the US National Academy of Engineering, the American Academy of Arts and Sciences, and the US National Academy of Inventors. He is a Fellow of the Royal Society of Chemistry. Marks has published 1250 peer-reviewed articles and holds 265 U.S. patents. He received a B.S. degree from the U. of Maryland and a Ph.D. from MIT.