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Metals and ligand reactivity: an introduction to the organic chemistry of metal complexes

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Bibliographic Details
Main Author:	Constable, Edwin C. 1955- (Author)
Format:	Book
Language:	German
Published:	Weinheim [u.a.] VCH 1996
Edition:	New, rev. and expanded ed.
Subjects:	Ligand Metallkomplexe Reaktivität
Links:	http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=006932228&sequence=000001&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA
Physical Description:	XIV, 308 S. Ill., graph. Darst.
ISBN:	3527292772 3527292780

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Record in the Search Index

DE-BY-TUM_call_number	0202 CHE 334f 2002 A 1790 0302 CHE 334f 1990 A 4949(1,2)
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adam_text	CONTENTS PREFACE TO THE SECOND EDITION . VII PREFACE TO THE FIRST EDITION VIII ABBREVIATIONS AND SOME COMMON LIGANDS XIII 1 INTRODUCTION 1 1.1 GENERAL 1 1.1.1 CO-ORDINATION COMPOUNDS 1 1.2 CRYSTAL FIELD THEORY 3 1.2.1 CRYSTAL FIELD STABILISATION ENERGIES 6 1.2.2 THE SPECTROCHEMICAL SERIES 6 1.2.3 THE NEPHELAUXETIC EFFECT 7 1.3 MOLECULAR ORBITAL AND LIGAND FIELD THEORIES 8 1.3.1 MOLECULAR WAVE FUNCTIONS AND VALENCE BOND THEORY 9 1.3.2 MOLECULAR ORBITAL THEORY 10 1.3.3 LIGAND FIELD THEORY 13 1.4 THE ELECTRONEUTRALITY PRINCIPLE 16 1.5 REPRISE 16 1.6 PRINCIPLES OF REACTIVITY AND MECHANISM 16 1.6.1 THERMODYNAMIC AND KINETIC CONSTRAINTS UPON REACTIVITY 17 1.7 SUMMARY 20 2 THE METAL-LIGAND INTERACTION 22 2.1 GENERAL 22 2.2 CONFORMATIONAL CHANGES 23 2.2.1 STERIC CONSEQUENCES OF METAL-LIGAND BONDING 24 2.2.2 GEOMETRICAL CONSEQUENCES OF CHELATION 25 2.2.3 CHEMICAL CONSEQUENCES OF LONE PAIR NON-AVAILABILITY 30 2.3 POLARISATION OF THE LIGAND 31 2.3.1 THE NATURE OF IONIC INTERACTIONS 32 2.3.2 ENHANCEMENT OF LIGAND POLARISATION - INTRINSIC EFFECTS , . 34 2.4 *-BONDING CHANGES 39 2.4.1 SYMMETRY AND REACTIVITY 40 2.5 CONCLUSIONS 44 3 REACTIONS OF CO-ORDINATED CARBONYL COMPOUNDS WITH NUCLEOPHILES 46 3.1 GENERAL 46 3.2 NUCLEOPHILIC ATTACK ON CO-ORDINATED ESTERS AND AMIDES 48 3.2.1 ATTACK BY CO-ORDINATED NUCLEOPHILE 49 3.3 HYDROLYSIS OF AMINO ACID ESTERS AND AMIDES 50 3.4 OTHER REACTIONS OF NUCLEOPHILES AND CARBONYL COMPOUNDS 57 3.5 CONCLUSIONS 62 4 OTHER REACTIONS OF CO-ORDINATED LIGANDS WITH NUCLEOPHILES 63 4.1 GENERAL 63 4.2 REACTIONS OF NUCLEOPHILES WITH SP HYBRIDISED CARBON CENTRES 65 4.2.1 NUCLEOPHILIC ATTACK ON CO-ORDINATED NITRILES 65 4.3 REACTIONS OF NUCLEOPHILES WITH SP 2 HYBRIDISED CARBON CENTRES 72 4.3.1 HYDROLYSIS OF IMINES 72 4.3.2 REDUCTION OF IMINES 78 4.3.3 REACTIONS OF CYANATES 78 4.4 REACTIONS OF NUCLEOPHILES WITH SP 3 HYBRIDISED CARBON CENTRES 80 4.4.1 HYDROLYSIS OF THIOETHERS AND RELATED REACTIONS 80 4.4.2 ARBUZOV REACTIONS 84 4.5 HYDROLYSIS OF PHOSPHATE ESTERS AND RELATED REACTIONS 85 4.6 CONCLUSIONS 87 5 STABILISATION OF ANIONS AND REACTIONS OF CO-ORDINATED LIGANDS WITH ELECTROPHILES 89 5.1 GENERAL INTRODUCTION 89 5.2 STABILISATION OF ENOLATES 89 5.3 REACTIVITY OF CO-ORDINATED ENOLATES WITH ELECTROPHILES 91 5.4 REACTIONS OF CO-ORDINATED AMINES 102 5.4.1 AMINE DEPROTONATION AND THE S N L CB MECHANISM 109 5.5 FORMATION AND REACTIVITY OF IMINES ILL 5.5.1 FORMATION BY CONDENSATION OF AN AMINE WITH A CARBONYL COMPOUND ... 112 5.5.2 TRANSIMINATION 116 5.6 REACTIONS OF CO-ORDINATED CYANIDE 119 5.7 REACTIONS OF CO-ORDINATED WATER OR HYDROXIDE 120 5.7.1 INTRAMOLECULAR ATTACK BY CO-ORDINATED HYDROXIDE 121 5.7.2 INTERMOLECULAR ATTACK BY CO-ORDINATED HYDROXIDE 127 5.8 REACTIONS OF CO-ORDINATED THIOLATE 128 5.9 OTHER REACTIONS OF ESTERS AND AMIDES WITH CO-ORDINATED NUCLEOPHILES . . 133 5.10 CONCLUSIONS . 134 6 CYCLIC LIGANDS AND THE TEMPLATE EFFECT 135 6.1 WHAT IS A MACROCYCLE? 135 6.1.1 THE SYNTHESIS OF LARGE CYCLIC MOLECULES 136 6.2 THE TEMPLATE METHOD 138 6.2.1 WHY USE TEMPLATE REACTIONS? 141 6.3 METAL ION CONTROL OF RING CLOSURE REACTIONS 142 6.3.1 NUCLEOPHILIC DISPLACEMENT 142 6.3.2 IMINE FORMATION 145 6.3.3 C-C BOND FORMATION 148 6.4 STOICHIOMETRY - [1+1], [2+2] OR OTHER? 150 6.5 THE MACROCYCLIC EFFECT 153 6.5.1 ORIGIN OF THE MACROCYCLIC EFFECT 154 6.6 METAL ION DEPENDENCE 158 6.6.1 MACROCYCLIC HOLE SIZE - AN ABUSED CONCEPT 158 6.7 CONSEQUENCES OF METAL ION/HOLE SIZE MISMATCH 162 6.7.1 THE METAL ION DOES NOT ACT AS A TEMPLATE 163 6.7.2 CONTROL OVER THE RING SIZE 163 6.7.3 CONFORMATIONAL CHANGE MAY ALTER THE APPARENT HOLE SIZE 165 6.7.4 MISMATCH IN SIZES MAKES THE METAL ION LABILE 167 6.7.5 METAL-DIRECTED REARRANGEMENT TO PRODUCE A MORE SUITABLE CAVITY .... 168 6.7.6 REARRANGEMENT RELATED TO CO-ORDINATION GEOMETRY 174 6.8 MULTICOMPONENT ASSEMBLY OF MACROCYCLES 175 6.9 INTO THE THIRD DIMENSION 179 6.10 CONCLUSIONS 180 7 THE THREE-DIMENSIONAL TEMPLATE EFFECT, SUPRAMOLECULAR CHEMISTRY AND MOLECULAR TOPOLOGY 183 7.1 THE THREE-DIMENSIONAL TEMPLATE EFFECT 183 7.2 TEMPLATE CONDENSATIONS AT KINETICALLY INERT OCTAHEDRAL METAL CENTRES . . 183 7.2.1 MOLECULAR TOPOLOGY 185 7.2.2 MORE ENCAPSULATING LIGANDS FROM TWO REACTANTS 187 7.2.3 ENCAPSULATING LIGANDS FROM MORE THAN TWO COMPONENTS 188 7.2.4 SOME MECHANISTIC AND STEREOCHEMICAL ASPECTS OF SEPULCHRATES AND RELATED ENCAPSULATING LIGANDS 199 7.3 SUPRAMOLECULAR CHEMISTRY 202 7.3.1 WHAT IS SUPRAMOLECULAR CHEMISTRY? 202 7.3.2 MOLECULAR RECOGNITION, COMPLEMENTARITY AND SELF-ASSEMBLY 205 7.3.3 METAL ION COMPLEMENTARITY AND METALLOSUPRAMOLECULAR CHEMISTRY .... 210 7.4 BUILDING HELICAL COMPLEXES 212 7.4.1 DOUBLE-HELICAL STRUCTURES 212 7.4.2 TRIPLE-HELICAL STRUCTURES 218 7.5 CATENANES - MOLECULAR DAISY CHAINS 221 7.6 TYING MOLECULES IN KNOTS 228 7.7 CONCLUSIONS 231 8 AROMATIC AND HETEROCYCLIC LIGANDS 233 8.1 INTRODUCTION 233 8.2 ELECTROPHILIC AROMATIC SUBSTITUTION 233 8.3 NUCLEOPHILIC AROMATIC SUBSTITUTION 236 8.4 HETEROAROMATIC LIGANDS 240 8.5 REACTIONS OF FIVE-MEMBERED HETEROCYCLES 241 8.6 NUCLEOPHILIC REACTIONS OF CO-ORDINATED PYRIDINES 245 8.7 ELECTROPHILIC REACTIONS OF CO-ORDINATED PYRIDINES 258 8.8 SUMMARY 261 9 OXIDATION AND REDUCTION OF CO-ORDINATED LIGANDS 263 9.1 INTRODUCTION - THE MEANING OF OXIDATION AND REDUCTION 263 9.2 OXIDATION BY LOSS OF ELECTRONS 265 9.3 OXIDATION BY C-H BOND CLEAVAGE 271 9.4 OXIDATION BY OXYGEN ATOM TRANSFER 278 9.5 SUMMARY 287 10 ENVOI 288
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author	Constable, Edwin C. 1955-
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indexdate	2024-12-20T09:53:35Z
institution	BVB
isbn	3527292772 3527292780
language	German
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physical	XIV, 308 S. Ill., graph. Darst.
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spellingShingle	Constable, Edwin C. 1955- Metals and ligand reactivity an introduction to the organic chemistry of metal complexes Ligand (DE-588)4035711-9 gnd Metallkomplexe (DE-588)4038898-0 gnd Reaktivität (DE-588)4208182-8 gnd
subject_GND	(DE-588)4035711-9 (DE-588)4038898-0 (DE-588)4208182-8
title	Metals and ligand reactivity an introduction to the organic chemistry of metal complexes
title_auth	Metals and ligand reactivity an introduction to the organic chemistry of metal complexes
title_exact_search	Metals and ligand reactivity an introduction to the organic chemistry of metal complexes
title_full	Metals and ligand reactivity an introduction to the organic chemistry of metal complexes Edwin C. Constable
title_fullStr	Metals and ligand reactivity an introduction to the organic chemistry of metal complexes Edwin C. Constable
title_full_unstemmed	Metals and ligand reactivity an introduction to the organic chemistry of metal complexes Edwin C. Constable
title_short	Metals and ligand reactivity
title_sort	metals and ligand reactivity an introduction to the organic chemistry of metal complexes
title_sub	an introduction to the organic chemistry of metal complexes
topic	Ligand (DE-588)4035711-9 gnd Metallkomplexe (DE-588)4038898-0 gnd Reaktivität (DE-588)4208182-8 gnd
topic_facet	Ligand Metallkomplexe Reaktivität
url	http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=006932228&sequence=000001&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA
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Call Number:	0202 CHE 334f 2002 A 1790 Floor plan
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Branch Library Chemistry

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Call Number:	0302 CHE 334f 1990 A 4949(1,2) Floor plan
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