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Max-Planck-Institut Für Kohlenforschung Report for The Max-Planck-Institut für Kohlenforschung Report for the Period of January 2002 – December 2004 Printed May 2005 Max-Planck-Institut für Kohlenforschung Kaiser-Wilhelm-Platz 1 45470 Mülheim an der Ruhr, Germany Tel. +49 208 3 06 1 Fax +49 208 3 06 29 80 http://www.mpi-muelheim.mpg.de Managing Director Professor Dr. Ferdi Schüth Director of the Department of Synthetic Organic Chemistry Professor Dr. Manfred T. Reetz Tel. +49 208 3 06 20 00 Fax +49 208 3 06 29 85 E-mail: [email protected] Director of the Department of Homogeneous Catalysis NN Director of the Department of Heterogeneous Catalysis Professor Dr. Ferdi Schüth Tel. +49 208 3 06 23 73 Fax +49 208 3 06 29 95 E-mail: [email protected] Director of the Department of Organometallic Chemistry Professor Dr. Alois Fürstner Tel. +49 208 3 06 23 42 Fax +49 208 3 06 29 94 E-mail: [email protected] Director of the Department of Theory Professor Dr. Walter Thiel Tel. +49 208 3 06 21 50 Fax +49 208 3 06 29 96 E-mail: [email protected] External Scientific Members of the Max-Planck-Institut für Kohlenforschung Professor Dr. Alois Haas Medonstrasse 17 14532 Kleinmachnow Germany Professor Dr. Jack Halpern University of Chicago Department of Chemistry 5735 South Ellis Avenue Chicago, Illinois 60637 USA Professor Dr. Walter Leitner Lehrstuhl für Technische Chemie und Petrolchemie Institut für Technische und Makromolekulare Chemie Rheinisch-Westfälische Technische Hochschule Aachen Worringer Weg 1 52074 Aachen Germany Member of the Scientific Council of the Max Planck Society, Section of Chemistry, Physics and Technology Professor Dr. Matthias W. Haenel (January 2002 - August 2003) Dr. Wolfgang Schmidt (since August 2003) Emeritus Scientific Members of the Max-Planck-Institut für Kohlenforschung Professor Dr. Günther Wilke Professor Dr. Roland Köster Table of Contents 1 The Max-Planck-Institut für Kohlenforschung 9 1.1 History 11 1.2 Current Research Areas 14 1.3 Organigram 2003 16 1.4 Members of the Scientific Advisory Board 17 1.5 Members of the Board of Governors 18 2 Research Programs 19 2.1 Department of Synthetic Organic Chemistry 21 2.1.1 Transition Metal Catalyzed Reactions ( M. T. REETZ ) 27 2.1.2 Directed Evolution as a Means to Create Enantioselective Enzymes (M. T. REETZ ) 31 2.1.3 Directed Evolution as a Means to Create Selective Hybrid Catalysts (M. T. REETZ ) 36 2.1.4 Nanosized Metal and Metal Oxide Colloids ( M. T. REETZ ) 39 2.1.5 Olefin Polymerization with Silica Supported Metallocene/MAO Catalysts (G. FINK ) 41 2.1.6 Metallocene-Catalyzed C7-Linkage in the Hydrooligomerization of Norbornene by σ-Bond Metathesis: Insight into the Microstructure of Polynorbornene ( G. FINK ) 44 2.1.7 Homo-, Co- and Terpolymerization of Different α-Olefins and Functionalized Monomers with Metallocenes and New Catalysts (G. FINK ) 47 2.1.8 New Transition Metal-Catalyzed Reactions for Organic Synthesis ( L. J. GOOSSEN ) 48 2.1.9 Hydrogenation/Hydrogenolysis of Bituminous Coals with Homogeneous Borane Catalysts ( M. W. HAENEL ) 52 2.1.10 Development of Thermostable Homogeneous Catalysts Based on Polycyclic Arenes and Heteroarenes ( M. W. HAENEL ) 54 2.1.11 Supercritical Carbon Dioxide as Reaction Medium for Catalysis (W. LEITNER / N. THEYSSEN ) 58 2.2 Department of Homogeneous Catalysis 63 2.2.1 Mononuclear and Polynuclear Transition Metal Complexes with Pentalene and Related Polycycles as Ligands ( K. JONAS ) 65 2.2.2 Organocatalytic Asymmetric α-Alkylation of Aldehydes (B. LIST ) 73 2.2.3 Organocatalytic Asymmetric Intramolecular Michael Reaction of Aldehydes ( B. LIST ) 75 2.2.4 Metal-Free Catalytic Hydrogenation ( B. LIST ) 77 2.2.5 Allyl Complexes of the d 10 -Metals Nickel and Palladium (K.-R. PÖRSCHKE ) 80 2.2.6 Stereochemical Nonrigidity of Ni- and Pd-allyl Complexes (K.-R. PÖRSCHKE ) 82 2.3 Department of Heterogeneous Catalysis 85 2.3.1 Understanding the Synthesis of Solid Catalysts ( F. SCHÜTH ) 91 2.3.2 Combinatorial Catalysis and Novel Reactor Concepts ( F. SCHÜTH ) 94 2.3.3 High Surface Area Catalyst Materials ( F. SCHÜTH ) 97 2.3.4 Light Metal Hydrides for Hydrogen and Energy Storage (F. SCHÜTH / B. BOGDANOVI Ć) 101 2.3.5 Nanostructured Metal Colloids ( H. BÖNNEMANN ) 104 2.3.6 Porous and Nanostructured Materials ( S. KASKEL ) 107 2.3.7 Nanostructured Optical Materials ( F. MARLOW ) 109 2.3.8 Novel Mesostructures ( F. MARLOW ) 111 2.4 Department of Organometallic Chemistry 113 2.4.1 Methathesis of Alkenes and Alkynes ( A. FÜRSTNER ) 118 2.4.2 Iron Catalyzed Cross Coupling Reactions ( A. FÜRSTNER ) 123 2.4.3 Novel Concepts for Catalysis ( A. FÜRSTNER ) 127 2.4.4 Catalysis Based Syntheses and Evaluation of Bioactive Natural Products ( A. FÜRSTNER ) 131 2.4.5 New Concepts for Catalysis ( F. GLORIUS ) 135 2.5 Department of Theory 139 2.5.1 Ab Initio Methods ( W. THIEL ) 143 2.5.2 Density Functional Methods ( W. THIEL ) 147 2.5.3 Semiempirical Methods ( W. THIEL ) 150 2.5.4 Combined Quantum Mechanical/Molecular Mechanical Methods (W. THIEL ) 153 2.5.5 Molecular Modeling ( K. ANGERMUND ) 157 2.5.6 Computational Chemistry of Transition-Metal Compounds ( M. BÜHL ) 159 3 Scientific Service Units 163 3.1 Technical Laboratories ( N. THEYSSEN ) 166 3.2 Chromatography and Separation Science ( D. BELDER ) 167 3.3 Mass Spectrometry ( W. SCHRADER ) 169 3.4 Nuclear Magnetic Resonance ( R. MYNOTT ) 171 3.5 Chemical Crystallography ( C. W. LEHMANN ) 173 3.6 Electron Microscopy ( B. TESCHE ) 175 3.7 Library and Information Management ( W. RICHTER ) 177 3.8 Computer Group ( A. KOSLOWSKI ) 178 4 The Training of Young Scientists 181 5 Technology Transfer 191 6 Special Events and Activities 195 6.1 Open House 197 6.2 60 th Birthday of Manfred T. Reetz 198 6.3 Visit of the Cabinet of the State Government 199 6.4 Other Events and Activities 200 7 Appendices 203 7.1 List of Publications 205 7.2 List of Invited Talks Given by Members of the Institute 231 7.3 Scientific Honors, Lectureships, Awards 246 7.4 Contacts with Universities 248 7.5 List of Talks Given by Guests 250 7.6 Alexander von Humboldt Senior Awardees Hosted by the Institute 257 7.7 Local Activities of the Young Chemists Forum (JCF) of the 258 German Chemical Society (GDCh) 7.8 How to Reach the Institute 260 CHAPTER 1 The Max-Planck-Institut für Kohlenforschung 9 10 History 1.1 History of the Max-Planck-Institut für Kohlenforschung The Kaiser-Wilhelm-Institut für Kohlenforschung (coal research) in Mülheim/Ruhr was founded in 1912 by the Kaiser Wilhelm Society, representatives of the coal industry and the town of Mülheim/Ruhr. In 1913 Franz Fischer (1877-1947), who in 1911 had been appointed professor for electrochemistry at the Technical University in Berlin- Charlottenburg, was chosen to be the first Director of the Institut für Kohlenforschung. Franz Fischer and his co-workers carried out basic research in a number of areas concerning the formation and chemical composition of coal as well as on its conversion into solid, liquid and gaseous products. The most important contribution culminated in the so-called Fischer-Tropsch process for coal liquefaction. In 1925, Franz Fischer and the group leader Hans Tropsch reported that liquid hydrocarbons (alkanes) can be produced from carbon monoxide and hydrogen in the presence of solid metal catalysts. The mixture of the two gases (synthesis gas) necessary for this new process was prepared by the "gasification" of coal with steam and oxygen at 900 °C. In 1925 the "Studien- und Verwertungsgesellschaft mbH" was founded for the purpose of exploiting the patents. By the early 1940s nine industrial plants were operating in Germany producing ca. 600 000 tons of liquid hydrocarbons per year. Today there is a renewed interest in Fischer-Tropsch technology with plants in Sasolburg/South Africa and in Malaysia. In 1939 Franz Fischer instigated a change in the status of the Institute and it became a foundation of private law with the objective of supporting the scientific investigation of coal for the public benefit. Following Fischer's retirement in 1943 Karl Ziegler (1898-1973) was appointed Director of the Institute. After the founding of the Max Planck Society as the successor of the Kaiser Wilhelm Society in 1948, the Institute obtained its present name in 1949. As a consequence of Ziegler's appointment, the main research efforts in the Institute shifted to organometallic chemistry. Based upon his earlier experience with the organic compounds of the alkali metals, Ziegler and his co-workers turned their attention to aluminum. In 1949 they reported the multiple addition of aluminum alkyls to ethylene which became known as the "Aufbau" reaction. The product of this oligomerization was a mixture of aluminum alkyls having long, linear alkyl chains attached to the metal and which could be converted into the corresponding α-olefins or primary alcohols, the latter being biodegradable detergents. An unexpected observation during the systematic investigation of this reaction led to the discovery that transition metals have a dramatic effect on the "Aufbau" reaction and, in particular, the addition of compounds of 11 History titanium or zirconium led to the coupling of up to 100 000 ethylene molecules at normal pressure and temperature. The optimized process employed the so-called organometallic "Mischkatalysatoren" consisting of an aluminum alkyl and a transition metal salt. It was patented in 1953 and led to a dramatic development of the industrial production of polyethylene and polypropylene as cheap and versatile polymers. The licensing of the patents enabled the Institute to be operated on an independent financial basis for nearly 40 years.
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