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|a 9783662450215
|9 978-3-662-45021-5
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|a 10.1007/978-3-662-45021-5
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|a Zhang, Shaoguang.
|e author.
|4 aut
|4 http://id.loc.gov/vocabulary/relators/aut
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|a The Chemistry of Zirconacycles and 2,6-Diazasemibullvalenes
|h [electronic resource] :
|b Synthesis, Structures, Reactions, and Applications in the Synthesis of Novel N-Heterocycles /
|c by Shaoguang Zhang.
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|a 1st ed. 2015.
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|a Berlin, Heidelberg :
|b Springer Berlin Heidelberg :
|b Imprint: Springer,
|c 2015.
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|a XI, 173 p. 131 illus., 5 illus. in color.
|b online resource.
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|a text
|b txt
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|a computer
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|a online resource
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|a text file
|b PDF
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|a Springer Theses, Recognizing Outstanding Ph.D. Research,
|x 2190-5061
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|a Introduction to Zirconacycle Chemistry -- Zirconocene-Mediated Cyclization of Bis(alkynyl)silanes and Nitriles: Synthesis of N-Heterocycles and Isolation, Characterization and Synthetic Application of Zr/Si-containing Reactive Intermediates -- Bulky-Nitrile Coordination Induced Skeleton Rearrangement of Zr/Si-containing Metallacycles and Selective Synthesis of 5-Azaindoles -- Introduction to Semibullvalenes and Azasemibullvalenes -- 2,6-Diazasemibullvalenes: Synthesis, Structure, Theoretical Analysis and Computational Chemistry -- 2,6-Diazasemibullvalenes: Reaction Chemistry and Synthetic Application.
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|a 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.
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|a Organometallic chemistry .
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|a Physical chemistry.
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|a Chemistry, Physical and theoretical.
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|a Crystallography.
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|a Organometallic Chemistry.
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|a Physical Chemistry.
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|a Theoretical Chemistry.
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|a Crystallography and Scattering Methods.
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|a SpringerLink (Online service)
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|t Springer Nature eBook
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|i Printed edition:
|z 9783662450222
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|i Printed edition:
|z 9783662450208
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|i Printed edition:
|z 9783662515143
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|a Springer Theses, Recognizing Outstanding Ph.D. Research,
|x 2190-5061
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|u https://doi.uam.elogim.com/10.1007/978-3-662-45021-5
|z Texto Completo
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|a ZDB-2-CMS
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|a ZDB-2-SXC
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|a Chemistry and Materials Science (SpringerNature-11644)
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|a Chemistry and Material Science (R0) (SpringerNature-43709)
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