By Carsten Bolm, F. Ekkehardt Hahn
Using secondary interactions for the activation of non-reactive substrates constitutes a brand new and smooth procedure in catalysis.
this primary finished remedy of this significant learn box covers the complete box and divulges the hyperlinks among a number of the chemical disciplines. It hence adopts an interdisciplinary method, making it of curiosity to the total chemical community.
A needs to for natural, inorganic, catalytic and complicated chemists, in addition to these operating with/on organometallics.Content:
Chapter 1 Chemistry of Metalated box Molecules (pages 1–15): Berthold Kersting
Chapter 2 The Chemistry of Superbasic Guanidines (pages 17–37): Jorg Sundermeyer, Volker Raab, Ekatarina Gaoutchenova, Udo Garrelts, Nuri Abacilar and Klaus Harms
Chapter three Iron Complexes and Dioxygen Activation (pages 39–51): Thomas Nebe, Jing?Yuan Xu and Siegfried Schindler
Chapter four Tuning of buildings and houses of Bispidine Complexes (pages 53–63): Peter Comba and Marion Kerscher
Chapter five Novel Phosphorus and Nitrogen Donor Ligands Bearing Secondary Functionalities for purposes in Homogeneous Catalysis (pages 65–88): Anna?Katharina Pleier, Yu solar, Anett Schubert, Dirk Zabel, Claudia may perhaps, Andreas Reis, Gotthelf Wolmershauser and Werner R. Thiel
Chapter 6 Square?Pyramidal Coordinated Phosphine Iron Fragments: A story of the unforeseen (pages 89–102): Andreas Grohmann and Stephan Kohl
Chapter 7 Regioselective Catalytic job of Complexes with NH, NR?Substituted Heterocyclic Carbene Ligands (pages 103–122): Siegfried R. Waldvogel, Anke Spurg and Prof. Dr. F. Ekkehardt Hahn
Chapter eight Functionalized Cycloheptatrienyl?Cyclopentadienyl Sandwich Complexes as construction Blocks in Metallo?Supramolecular Chemistry (pages 123–146): Matthias Tamm
Chapter nine Monosaccharide Ligands in Organotitanium and Organozirconium Chemistry (pages 147–164): Peter Kitaev, Daniela Zeysing and Jurgen Heck
Chapter 10 Reactions of C?F Bonds with Titanocene and Zirconocene: From Secondary interplay through Bond Cleavage to Catalysis (pages 165–182): Uwe Rosenthal, Vladimir V. Burlakov, Perdita Arndt, Anke Spannenberg, Ulrike Jager?Fiedler, Marcus Klahn and Marko Hapke
Chapter eleven Bisazines within the Coordination Sphere of Early Transition Metals (pages 183–207): Ruediger Beckhaus
Chapter 12 Bifunctional Molecular platforms with Pendant Bis(pentafluorophenyl)boryl teams: From Intramolecular CH?Activation to Heterolytic Dihydrogen Splitting (pages 209–230): Michael Hill, Christoph Herrmann, Patrick Spies, Gerald Kehr, Klaus Bergander, Roland Frohlich and Gerhard Erker
Chapter thirteen Ruthenium?Containing Polyoxotungstates: constitution and Redox job (pages 231–243): Ulrich Kortz
Chapter 14 From NO to Peroxide Activation by way of version Iron(III) Complexes (pages 245–272): Alicja Franke, Natalya Hessenauer?Ilicheva, Joo?Eun Jee and Rudi van Eldik
Chapter 15 artificial Nitrogen Fixation with Molybdenum and Tungsten Phosphine Complexes: New advancements (pages 273–296): Gerald Stephan and Felix Tuczek
Chapter sixteen Directed C?H Functionalizations (pages 297–312): Prof. Dr. Carsten Bolm
Chapter 17 improvement of Novel Ruthenium and Iron Catalysts for Epoxidation with Hydrogen Peroxide (pages 313–337): guy kinfolk Tse, Bianca Bitterlich and Matthias Beller
Chapter 18 Pentacoordinating Bis(oxazoline) Ligands with Secondary Binding websites (pages 339–348): Caroline A. Schall, Michael Seitz, Anja Kaiser and Oliver Reiser
Chapter 19 Flavin Photocatalysts with Substrate Binding websites (pages 349–358): Harald Schmaderer, Jiri Svoboda and Burkhard Konig
Chapter 20 New Catalytic Cu?, Pd? and Stoichiometric Mg?, Zn?Mediated Bond Activations (pages 359–377): Tobias Thaler, Hongjun Ren, Nina Gommermann, Giuliano C. Clososki, Christoph J. Rohbogner, Stefan H. Wunderlich and Paul Knochel
Chapter 21 From Cobalt(II)?Activated Molecular Oxygen to Hydroxymethyl?Substituted Tetrahydrofurans (pages 379–396): Barbara Menendez Perez, Dominik Schuch and Jens Hartung
Chapter 22 Regiodivergent Epoxide beginning (pages 397–409): Andreas Gansauer, Florian Keller, Chun?An Fan and Peter Karbaum
Chapter 23 Supramolecular packing containers: Host?Guest Chemistry and Reactivity (pages 411–425): Markus Albrecht
Chapter 24 Self?Assembly of Dinuclear Helical Metallosupramolecular Coordination Compounds (pages 427–446): Ulf Kiehne, Jens Bunzen and Arne Lutzen
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Additional info for Activating Unreactive Substrates: The Role of Secondary Interactions
Numbers in parentheses refer to yields of isolated products. 10). 5 days) and affords only two products, 40a and 40b, in a ratio of 57:43. The products 36a,b can be liberated via acid hydrolysis. Thus, in striking contrast to the low regioselectivity observed in the background reaction, the Diels–Alder reaction between the encapsulated dienoate and acrylonitrile proceeds with strict meta regioselectivity. In addition, no by-products are detected. 10 Preparation of complexes 40a,b and Diels-Alder products 36a,b.
1 could be analyzed in great detail and were studied independently mainly by the research groups of Que and Lippard [8–12]. 1 Dinuclear iron-peroxo complexes with the ligands HTPMP, HPTP and Et-HPTB. 1 . Furthermore, in cooperation with the Krebs group, we could show that the same complexes can be prepared much more easily from the relevant iron(III) complexes and hydrogen peroxide . These reactions could be investigated in protic solvents at ambient temperatures, and it turned out that the product complexes were much more persistent under these conditions (hours in contrast to seconds).
The secondary chelate effect increases basicity of guanidines by about 4 orders and of phosphazenes by nearly 9 orders of magnitude! Because of the secondary intramolecular interaction, HMPN becomes about two orders of magnitude more basic than monodentate Schwesinger base tert-Bu-P1. 3 Some Perspectives in Proton Sponge Chemistry TMGN, despite its narrow bite angle, can be used as a constrained chelate ligand to metal cations such as Be2þ and even to larger coinage and platinum metals . We believe that a combination of the strong donor capability, steric strain and demand will lead to unusual properties of corresponding complexes.