Brown University School of Engineering

Dr. Michael Limbach Lecture, BASF--The Chemical Company, Center for Chemical Innovation

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Tuesday, August 06, 2013 12:00pm - 1:00pm

Dr. Michael Limbach Lecture, BASF--The Chemical Company, Center for Chemical Innovation Tuesday, August 6th Barus and Holey Room 190 12:00pm Dr. Michael Limbach Dr. Michael Limbach studied chemistry at the Technische Universität Karlsruhe (TH) and the Georg-August-Universität Göttingen (both Germany) and obtained his Dr. rer. nat. in 2004 from the latter in the field of organic synthesis under the supervision of A. de Meijere. From late in 2004 to 2006 he worked as a postdoctoral fellow with D. Seebach at ETH Zürich (Switzerland) on the elucidation of reaction mechanisms in asymmetric organocatalysis. Late in 2006 he joined BASF’s Process Research & Chemical Engineering (“Ammoniaklaboratorium”) to work on oxidation reactions and olefin metathesis. Since early in 2010 he is leading the Catalysis Research Laboratory (CaRLa), BASF’s joined laboratory for homogene-ous catalysis at the University of Heidelberg (Germany). At CaRLa he and the in-volved professors are working together with an international team of each six post-graduate scientists from the university and from BASF on the direct synthesis of acrylates from CO2 and alkenes – amongst other challenging reactions. For further information, see www.carla-hd.de. Acrylates from Alkenes and CO2, the Stuff that Dreams are Made of For more than three decades the catalytic synthesis of acrylates from the cheap and abundantly available C1 building block CO2 and alkenes has been an un-solved problem in catalysis research, both in academia and industry. Acrylates and their downstream products are ubiquitous in daily life as hygiene products, coatings, adhesives or plastics etc. and they are manufactured globally on a multi million ton level. Thus, a CO2-based route to such world-scale chemicals is econom-ically most attractive, but, due to thermodynamic and kinetic hurdles, also highly challenging. Since the revolutionary work of Hoberg,[1] nickelalactones (1) are dis-cussed as possible intermediates in a hypothetic catalytic cycle but i) an oxidative coupling of CO2 and ethylene has so far only been observed for selected ligands at low temperature (A), ii) despite first attempts,[2,3] the productive b-H elimination (B) is unknown as are, iii) Nickel acrylate complexes (C), and iv) the final ligand ex-change of p-complexes to ethylene to re-initiate the cycle (D). The first homogeneous catalyst system ever based on a Ni-complex is pre-sented. It permits the clearly catalytic synthesis of Na-acrylate from CO2, ethylene and a base, as demonstrated by a TON > 10 at this stage.[4] [1] H. Hoberg, Y. Peres, C. Krüger, Y. H. Tsay, Angew. Chem. Int. Ed. 1987, 26, 771-773. [2] R. Fischer, J. Langer, A. Malassa, D. Walther, H. Görls, G. Vaughan, Chem Commun. 2006, 2510-2512. [3] C. Bruckmeier, M. W. Lehenmeier, R. Reichardt, S. Vagin, B. Rieger, Organometallics 2010, 29, 2199-2202; S. Y. T. Lee, M. Cokoja, M. Drees, Y. Li, J. Mink, W. A. Herrmann, F. E. Kühn, ChemSusChem 2011, 4, 1275-1279. [4] M. L. Lejkowski, R. Lindner, T. Kageyama, G. É. Bódizs, P. N. Plessow, I. B. Müller, A. Schäfer, F. Rominger, P. Hofmann, C. Futter, S. A. Schunk, M. Limbach, Chem. Eur. J. 2012, 18, 14017-14025. Sponsored by the Center for Chemical Innovation: an IMNI Grant (the Institute for Molecular and Nanoscale Innovation) Brown University Host Professor Wesley Bernskoetter CCI@brown.edu • Phone: 401.863.3607