Max-Planck-Institut für Kohlenforschung Report for the Period of January 2011 – December 2013 confidential Printed January 2014 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.kofo.mpg.de Managing Director Professor Dr. Benjamin List Director of the Department of Homogeneous Catalysis Professor Dr. Benjamin List Tel. +49 208 3 06 24 10 Fax +49 208 3 06 29 99 E-mail: [email protected] 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] Director of the Department of Organic Synthesis Professor Dr. Manfred Reetz (until 2011) Tel. +49 6421 28 25 500 Fax +49 6421 28 25 620 E-mail: [email protected] Emeritus Scientific Members of the Max-Planck-Institut für Kohlenforschung Professor Dr. Günther Wilke Professor Dr. Roland Köster (deceased, June 2009) Professor Dr. Manfred Reetz (since 2011) 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 Members of the Scientific Council of the Max Planck Society, Section of Chemistry, Physics and Technology Dr. Claudia Weidenthaler (July 2009 – July 2012) Dr. Christian Lehmann (since July 2012) Table of Contents 1 The Max-Planck-Institut für Kohlenforschung 9 1.1 History 11 1.2 Current Research Areas 14 1.3 Organigram 2013 16 1.4 Members of the Scientific Advisory Board 17 1.5 Members of the Board of Governors 20 2 Research Programs 21 2.1 Department of Synthetic Organic Chemistry 23 2.1.1 Methodology Development in Directed Evolution (M. T. REETZ) 28 2.1.2 Applications of Advanced Directed Evolution Methods (M. T. REETZ) 34 2.1.3 Learning from Directed Evolution (M. T. REETZ) 41 2.1.4. Constructing Designer Cells for Enzymatic Cascade Reactions Based on Directed Evolution (M. T. REETZ) 46 2.1.5 Development of Novel Catalyst Systems for Epoxidation Reactions (W. LEITNER, N. THEYSSEN) 50 2.1.6 Publications from the Department of Synthetic Organic Chemistry 53 2.2 Department of Homogeneous Catalysis 55 2.2.1 Catalysis with chiral imidodiphosphates (B. LIST) 60 2.2.2 Organotextile Catalysis (B. LIST) 65 2.2.3 Activation of Carboxylic Acids in Organocatalysis (B. LIST) 70 2.2.4 Lewis Acid Organocatalysis (B. LIST) 75 2.2.5 Secondary Amine Catalysis (B. LIST) 80 2.2.6 The [3,3]-Diaza Cope Rearrangement in Asymmetric Catalysis (B. LIST) 85 2.2.7 Oxidative Coupling Reactions – Methods and Mechanisms (M. KLUSSMANN) 91 2.2.8 Electrophilic Domino Rearrangements of Keteniminium Derivatives (N. MAULIDE) 96 2.2.9 Catalytic Stereoselective Synthesis and Chemistry of Cyclobutenes (N. MAULIDE) 101 2.2.10 New Perspectives in Sulfur(IV) Chemistry (N. MAULIDE) 106 2.2.11 Redox-Neutral C–C bond forming reactions (N. MAULIDE) 112 2.2.12 Bispidine analogs of Cisplatin, Carboplatin, and Oxaliplatin (K.-R. PÖRSCHKE) 115 2.2.13 Structure and Solubility of 4-Oxopiperidinium Salts (K.-R. PÖRSCHKE) 119 2.2.14 Ni(0) Complexes of Polyunsaturated Aza Ligands (K.-R. PÖRSCHKE) 122 2.2.15 Publications from the Department of Homogeneous Catalysis 124 2.3 Department of Heterogeneous Catalysis 135 2.3.1 Nanoengineered Catalysts (F. SCHÜTH) 144 2.3.2 High Surface Area Materials (F. SCHÜTH) 149 2.3.3 Novel Catalytic Concepts (F. SCHÜTH) 154 2.3.4 Hydrides for Hydrogen and Energy Storage (F. SCHÜTH /M. FELDERHOFF) 158 2.3.5 Nanostructured Optical Materials (F. MARLOW) 161 2.3.6 Deep Depolymerization of Lignocelluloses by Mechanocatalysis (R. RINALDI / F. SCHÜTH) 163 2.3.7 New Catalytic Methodologies for Valorization of Lignin (R. RINALDI) 168 2.3.8 Understanding the Mechanisms of Dissolution and Hydrolysis of Cellulose in Electrolytes (R. RINALDI) 173 2.3.9 Formation of Nanoporous Silicates (W. SCHMIDT) 176 2.3.10 Photocatalysis on Transition Metal containing Microporopus Silicates (W. SCHMIDT) 180 2.3.11 Supported Transition Metal Oxide Catalysts for Low Temperature Application (W. SCHMIDT) 182 2.3.12 Design of Nanostructured Materials with High Surface Area for Photo- Electrochemical Water Splitting (H. TÜYSÜZ) 184 2.3.13 Advanced X-ray Diffraction Techniques (C. WEIDENTHALER) 189 2.3.14 Publications from the Department of Heterogeneous Catalysis 194 2.4 Department of Organometallic Chemistry 203 2.4.1 Metathesis (A. FÜRSTNER) 208 2.4.2 π-Acid Catalysis (A. FÜRSTNER) 213 2.4.3 New Reaction Modes (A. FÜRSTNER) 219 2.4.4 Catalysis Based Syntheses and Evaluation of Bioactive Natural Products (A. FÜRSTNER) 223 2.4.5 Cationic Ligands: Synthesis and Applications of Extreme π-Acid Catalysts (M. ALCARAZO) 229 2.4.6 Synthesis and applications of simultaneous -and -donor ligands: C-M dative double bonds (M. ALCARAZO) 234 2.4.7 Metal-free hydrogenations (M. ALCARAZO) 237 2.4.8 Publications from the Department of Organometallic Chemistry 240 2.5 Department of Theory 243 2.5.1 Ab Initio Methods (W. THIEL) 248 2.5.2 Density Functional Methods (W. THIEL) 253 2.5.3 Semiempirical Methods (W. THIEL) 259 2.5.4 Combined Quantum Mechanical / Molecular Mechanical Methods (W. THIEL) 264 2.5.5 Photoinduced Processes in Organic Molecules (M. BARBATTI) 272 2.5.6 Development and Assessment of Methods 276 2.5.7 Molecular Interactions in Organic and Biological Systems. Applications and Methodological Implementations (E. SÁNCHEZ-GARCÍA) 279 2.5.8 Publications from the Department of Theory 286 3 Scientific Service Units 293 3.1 Technical Laboratories (N. THEYSSEN) 296 3.2 Chromatography and Separation Science (P. SCHULZE) 298 3.3 Mass Spectrometry (W. SCHRADER) 300 3.4 Nuclear Magnetic Resonance (R. MYNOTT / C. FARÈS) 305 3.5 Electron Microscopy and Chemical Crystallography (C. W. LEHMANN) 310 3.6 Library and Information Management (P. FISCHER / R. BARABASCH) 316 3.7 Computer Group (P. FISCHER) 318 4 The Training of Young Scientists 323 5 Equal Opportunities 333 6 Personnel and Finances 337 6.1 Personnel 339 6.1.1 The Structure of the Work Force 339 6.1.2 Research Departments 341 6.1.3 Independent Junior Research Groups 343 6.1.4 Central Scientific Service Units 344 6.1.5 Administration and General Services 345 6.2 Finances 347 6.2.1 Research Budget 347 6.2.2 Third Party Funds 348 6.3 Facilities 360 7 Technology Transfer 361 8 Appendices 367 8.1 List of Publications 369 8.2 List of Invited Talks Given by Members of the Institute 417 8.3 Scientific Honors, Name Lectureships, Awards 442 8.4 Contacts with Universities 446 8.5 Special Events and Activities 450 8.5.1 Symposia at the Institute 453 8.6 List of Talks Given by Guests 458 8.7 Local Activities of the Young Chemists Forum (JCF) of the German Chemical Society (GDCh) 481 8.8 Public Relations (S.-L. GOMBERT) 485 8.9 Special Equipment 490 8.10 How to Reach the Institute 493 CHAPTER 1 The Max-Planck-Institut für Kohlenforschung 9 10 History 1.1 History The decision to found a Kaiser-Wilhelm-Institut für Kohlenforschung (coal research) in Mülheim/Ruhr was taken 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 as the first Director. 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, Malaysia, and Qatar (using natural gas instead of coal). In 1939 Franz Fischer instigated a change in the status of the Institute; 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.