Clathrochelates (eBook)

Synthesis, Structure and Properties

N.A. Kostromina, R.K. Kramer, Y.Z. Voloshin (Autoren)

eBook Download: PDF

2002 | 1. Auflage
432 Seiten
Elsevier Science (Verlag)
978-0-08-052917-2 (ISBN)

Infos

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.

Inhalt

Front Cover 1
Clathrochelates: Synthesis, Structure and Properties 4
Copyright Page 5
Table of Contents 12
Chapter 1. Fundamental concepts of complexes with encapsulated metal ions 14
1.1. Classification of macropolycyclic ligands 15
1.2. Nomenclature, abbreviations and classification of clathrochelates 17
Chapter 2. Synthesis of clathrochelates 24
2.1. Synthesis of macrobicyclic tris-dioximates 26
2.2. Synthesis of macrobicyclic phosphorus-containing d-metal tris-diiminates 76
2.3. Synthesis of sepulchrates and sarcophaginates 78
2.4. Synthesis of polyene and other types of clathrochelate complexes 127
Chapter 3. Spatial and electronic structure of clathrochelates 150
3.1. Sarcophaginates and sepulchrates 152
3.2. Macrobicyclic phosphorus-containing d-metal tris-diiminates 182
3.3. Macrobicyclic d-metal tris-dioximates 189
3.4. Polyene and other types of clathrochelate complexes 249
Chapter 4. Kinetics and mechanism of synthesis and decomposition of clathrochelates 262
4.1. Experimental approaches 263
4.2. Reactions of boron-capped iron(II) dioximates 269
4.3. Reactions of sarcophaginates and sepulchrates 280
Chapter 5. Properties of clathrochelates 293
5.1. Ion association of clathrochelates in solution 293
5.2. Electron-transfer processes in macrobicyclic complexes 308
5.3. Photochemical properties of macrobicyclic complexes 361
Chapter 6. Application possibilities of clathrochelate chemistry 393
Chapter 7. New types of clathrochelates: perspectives of synthesis 398
7.1. Ribbed-functionalized d-metal tris-dioximates 398
7.2. Mononuclear and polynuclear a-dioximates and a-oximehydrazonates obtained by capping with several p-block elements (arsenic, bismuth, and some others), d- and f-elements 403
7.3. Macrobicyclic Schiff bases formed by capping with Lewis acids 407
7.4. Clathrochelate complexes formed by the analogs of a-dioximes and a-oximehydrazones 409
7.5. Superclathrochelate structures 413
References 414
Subject index 430

Produkt-Details

• Erscheint lt. Verlag: 19.9.2002
• Sprache: englisch
• Themenwelt: Schulbuch / Wörterbuch
• Themenwelt: Naturwissenschaften ► Chemie ► Anorganische Chemie
• Themenwelt: Technik ► Umwelttechnik / Biotechnologie
• ISBN-10: 0-08-052917-8 / 0080529178
• ISBN-13: 978-0-08-052917-2 / 9780080529172