Elsevier S & T

Clathrochelates: Synthesis, Structure and Properties

Voloshin, Y.Z.; Kostromina, N.A.; Krämer, R.K.

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Table of contents
  • Cover
  • Table of Contentsxi
  • Chapter 1. Fundamental concepts of complexes with encapsulated metal ions1
  • 1.1. Classification of macropolycyclic ligands2
  • 1.2. Nomenclature, abbreviations and classification of clathrochelates4
  • Chapter 2. Synthesis of clathrochelates11
  • 2.1. Synthesis of macrobicyclic tris-dioximates13
  • 2.2. Synthesis of macrobicyclic phosphorus-containing d-metal tris-diiminates63
  • 2.3. Synthesis of sepulchrates and sarcophaginates65
  • 2.4. Synthesis of polyene and other types of clathrochelate complexes114
  • Chapter 3. Spatial and electronic structure of clathrochelates137
  • 3.1. Sarcophaginates and sepulchrates139
  • 3.2. Macrobicyclic phosphorus-containing d-metal tris-diiminates169
  • 3.3. Macrobicyclic d-metal tris-dioximates176
  • 3.4. Polyene and other types of clathrochelate complexes236
  • Chapter 4. Kinetics and mechanism of synthesis and decomposition of clathrochelates249
  • 4.1. Experimental approaches250
  • 4.2. Reactions of boron-capped iron(II) dioximates256
  • 4.3. Reactions of sarcophaginates and sepulchrates267
  • Chapter 5. Properties of clathrochelates280
  • 5.1. Ion association of clathrochelates in solution280
  • 5.2. Electron-transfer processes in macrobicyclic complexes295
  • 5.3. Photochemical properties of macrobicyclic complexes348
  • Chapter 6. Application possibilities of clathrochelate chemistry380
  • Chapter 7. New types of clathrochelates: perspectives of synthesis385
  • 7.1. Ribbed-functionalized d-metal tris-dioximates385
  • 7.2. Mononuclear and polynuclear α-dioximates and α-oximehydrazonates obtained by capping with sev390
  • 7.3. Macrobicyclic Schiff bases formed by capping with Lewis acids394
  • 7.4. Clathrochelate complexes formed by the analogs of α-dioximes and α-oximehydrazones396
  • 7.5. Superclathrochelate structures400
  • References401
  • Subject index417
Book details
  • Vendor Elsevier S & T
  • SKU 9780444512239
  • ISBN-13 9780080529172
  • Author Voloshin, Y.Z.; Kostromina, N.A.; Krämer, R.K.
  • Category Science
  • Subject Inorganic

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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.