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Synthesis, Structure and Properties
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By
Y.Z. Voloshin, Karpov Inst. Physical Chemistry, 10 Vorontsovo Pole, 103064 Moscow, Russia
N.A. Kostromina, Vernadskii Inst. General and Inorganic Chemistry, Kiev-142 03680, Ukraine
R.K. Kr mer, Anorganisch-Chemisches Institut, Ruprecht-arls Universität, Heidelberg, Im Neuenheimer Feld 270, 60129 Heidelberg, Germany
Description
Clathrochelates are compounds which contain a metal ion encapsulated within a three dimensional cage of macrobicyclic ligand atoms. Within
this cage the metal has unique properties and is to a great extent isolated from environmental factors. Such complexes are suitable as
models of the most essential biological systems, membrane transport, electron carriers, highly selective and sensitive analytical reagents,
catalysts for photochemical and redox processes, cation and anion receptors, etc. The aim of this monograph is to generalize and analyze
experimental and theoretical data on clathrochelates in order to promote further research in this promising field of chemistry.
Chapter
1 gives general concepts of complexes with encapsulated metal ions, discusses basic specific features of these compounds, considers and
characterizes the main types of compounds with encapsulated metal ions and the main classes of clathrochelates, and includes the current
nomenclature. Chapter 2 deals with the pathways of clathrochelate synthesis and the general procedures for the synthesis of macrobicyclic
tris-dioximates, phosphorus-containing tris-diiminates, sepulchrates, sarcophagi-nates, and polyene and other types of clathrochelate
complexes. Chapter 3 concerns studies of the electronic and spatial structure of clathrochelate complexes. In Chapter 4, the kinetics
and mechanism of synthesis and decomposition reactions of macrobicyclic tris-dioximates, sarcophaginates, and sepulchrates in solution
and gas phases are discussed. Chapter 5 considers the electrochemical, photochemical, and some other characteristics of clathrochelates
and their applications associated with these characteristics. Finally, the practical applications of the unique properties of clathrochelates
and perspectives on the synthesis of new clathrochelates are described in Chapters 6 and 7, respectively.
Audience
For chemists and biochemists in academia and industry.
Contents
Selected Papers
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Fundamental Concepts of Complexes with Encapsulated Metal Ions
. Classification of macropolycyclic
ligands. Nomenclature, abbreviations and classification of clathrochelates.
Synthesis of Clathrochelates
. Synthesis
of macrobicyclic tris-dioximates. Synthesis of macrobicyclic phosphorus-containing d-metal tris-diiminates. Synthesis of sepulchrates
and sarcophaginates. Synthesis of polyene and other types of clathrochelate complexes.
Spatial and Electronic Structure
of Clathrochelates
. Sarcophaginates and sepulchrates. Macrobicyclic phosphorus-containing d-metal tris-diiminates. Macrobicyclic
d-metal tris-dioximates. Polyene and other types of clathrochelate complexes.
Kinetics and Mechanism of Synthesis and
Decomposition of Clathrochelates
. Experimental approaches. Reactions of boron-capped iron(II) dioximates. Reactions of sarcophaginates
and sepulchrates.
Properties of Clathrochelates
. Ion association of clathrochelates in solution. Electron-transfer
processes in macrobicyclic complexes. Photochemical properties of macrobicyclic complexes.
Application Possibilities of
Clathrochelate Chemistry
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New Types of Clathrochelates: Perspectives of Synthesis
. Ribbed-functionalized d-metal tris-dioximates. Mononuclear and polynuclear α-dioximates and -αoximehydrazonates obtained by capping with several p-block elements (arsenic, bismuth, and some others), d- and f-elements. Macrobicyclic Schiff bases formed
by capping with Lewis acids. Clathrochelate complexes formed by the analogs of α-dioximes and α-oximehydrazones. Superclathrochelate
structures.
| Bibliographic details |
Hardbound, 432 pages, publication date: SEP-2002
ISBN-13: 978-0-444-51223-9
ISBN-10: 0-444-51223-3
Imprint: ELSEVIER
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Last update: 30 Nov 2009
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