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Metal carbene complexes have made their way from organometallic curiosities to valuable reagents and catalysts. They offer novel synthetic opportunities in carbon-carbon bond formation based on either carbene-centered reactions or on metal-templated processes which makes them indispensable in modern synthetic methodology. The most prominent metal carbenes are now either commercially available or easy to synthesize and handle with modern laboratory techniques. This volume organized in eight chapters written by the leading scientists in the field illustrates the theoretical background, non-classical nucleophilic and cycloaddition patterns, chromium-templated benzannulation and photo-induced reactions, rhodium-catalyzed carbene transfer as well as the principles and applications of olefin metathesis which has coined the progress in synthetic methodology over the past decade. Designed for researchers in academia and industry as well as graduate students it presents the state-of-the-art potential of carbene complexes in modern organic synthesis.
In this thesis, the author introduces two strategies used to construct various types of N-heterocycles, based on the chemistry of zirconacycles and 2,6-diazasemibullvalenes. In the first part, the author presents the development of multi-component cyclization of a zirconacyclobutene-silacyclobutene fused compound, nitriles and unsaturated compounds. These reactions provide synthetically useful methodology for various N-heterocycles such as 3-acyl pyrrole, pyrrolo[3,2-d]pyridazine and dihydropyrroloazepine, which are all difficult to synthesize by other means. The isolation and characterization of the key three-fused-ring Zr/Si-containing intermediates are also described in detail. These results show that the zirconacyclobutene-silacyclobutene fused compound behaves as a “chemical transformer” upon treatment with various substrates via the “coordination-induced skeleton rearrangement” mechanism. In the second part, the author demonstrates the synthesis and isolation of a series of 2,6-diazasemibullvalenes (NSBVs) from the reaction of 1,4-dilithio-1,3-dienes and nitriles, highlighting the significant progress made for the first time in this work: (1) determination of X-ray crystal structure of a substituted 2,6-diazasemibullvalene; (2) measurement of the activation barrier of its rapid intramolecular aza-Cope rearrangement in solution; (3) exploration of several reaction types of NSBV with diverse ring-expansion products and “bowl-shape” or “cage-shape” N-containing polycyclic skeletons; (4) demonstration of the localized structure as the predominant form and the homoaromatic delocalized structure as a minor component in the equilibrium using theoretical analysis. Based on well-founded results, this work sheds new light on this controversial topic.
Contents: Yves Canac and Remi Chauvin: Neutral eta1-carbon ligands: beyond carbon monoxide; Esteban P. Urriolabeitia: Ylide Ligands; Wolfgang Petz and Gernot Frenking: Carbodiphosphoranes and related ligands; Mareike C. Jahnke and F. Ekkehardt Hahn: Chemistry of N-Heterocyclic Carbene Ligands; Tsuyoshi Kato, Eddy Maerten, Antoine Baceiredo: Non-NHCs stable singlet carbene ligands; Victorio Cadierno, Sergio E. García-Garrido: All-Carbon-Substituted Allenylidene and Related Cumulenylidene Ligands; Victorio Cadierno, Sergio E. García-Garrido: Heteroatom-Conjugated Allenylidene and Related Cumulenylidene Ligands.
This volume is part of the series on "Chemical Thermodynamics", published under the aegis of the OECD Nuclear Energy Agency. It contains a critical review of the literature on thermodynamic data for inorganic compounds of zirconium. A review team, composed of five internationally recognized experts, has critically reviewed all the scientific literature containing chemical thermodynamic information for the above mentioned systems. The results of this critical review carried out following the Guidelines of the OECD NEA Thermochemical Database Project have been documented in the present volume, which contains tables of selected values for formation and reaction thermodynamical properties and an extensive bibliography.* Critical review of all literature on chemical thermodynamics for compounds and complexes of Zr.* Tables of recommended Selected Values for thermochemical properties* Documented review procedure* Exhaustive bibliography* Intended to meet requirements of radioactive waste management community* Valuable reference source for the physical, analytical and environmental chemist.
What is the difference between a compound and a mixture? How do we know what atoms and molecules look like? Who first organized into the periodic table? This title explores how atoms and molecules combine to form elements and compounds , why they are given the names that they have, and how they are used in our everyday lives. You will also find several experiments that can be done at home.
A readable, informative, fascinating entry on each one of the 100-odd chemical elements, arranged alphabetically from actinium to zirconium. Each entry comprises an explanation of where the element's name comes from, followed by Body element (the role it plays in living things), Element ofhistory (how and when it was discovered), Economic element (what it is used for), Environmental element (where it occurs, how much), Chemical element (facts, figures and narrative), and Element of surprise (an amazing, little-known fact about it). A wonderful 'dipping into' source for the familyreference shelf and for students.