Introduction to coordination chemistry:
Gespeichert in:
| 1. Verfasser: | |
|---|---|
| Format: | Buch |
| Sprache: | English |
| Veröffentlicht: |
Chichester
Wiley
2010
|
| Ausgabe: | 1. publ. |
| Schriftenreihe: | A Wiley textbook series
Inorganic chemistry |
| Schlagworte: | |
| Online-Zugang: | Inhaltsverzeichnis Klappentext |
| Beschreibung: | XIII, 290 S. Ill., graph. Darst. |
| ISBN: | 9780470519318 9780470519301 |
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| 100 | 1 | |a Lawrance, Geoffrey A. |e Verfasser |4 aut | |
| 245 | 1 | 0 | |a Introduction to coordination chemistry |c Geoffrey A. Lawrance |
| 250 | |a 1. publ. | ||
| 264 | 1 | |a Chichester |b Wiley |c 2010 | |
| 300 | |a XIII, 290 S. |b Ill., graph. Darst. | ||
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| 490 | 0 | |a A Wiley textbook series | |
| 490 | 0 | |a Inorganic chemistry | |
| 650 | 0 | |a Coordination compounds | |
| 650 | 4 | |a Coordination compounds | |
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Datensatz im Suchindex
| _version_ | 1804140749676085248 |
|---|---|
| adam_text | Contents
Preface
............................................ ix
Preamble
...........................................
xi
1
The Central Atom
.................................... 1
1.1
Key Concepts in Coordination Chemistry
....................... 1
1.2
A Who s Who of Metal Ions
............................. 4
1.2.1
Commoners and Uncommoners
....................... 5
1.2.2
Redefining Commoners
............................ 7
1.3
Metals in Molecules
................................. 9
1.3.1
Metals in the Natural World
.......................... 10
1.3.2
Metals in Contrived Environments
....................... 11
1.3.3
Natural or Made-to-Measure Complexes
.................... 12
1.4
The Road Ahead
................................... 13
Concept Keys
.................................... 14
Further Reading
................................... 14
2
Ligands
......................................... 15
2.1
Membership: Being a Ligand
............................. 15
2.1.1
What Makes a Ligand?
............................ 15
2.1.2
Making Attachments
-
Coordination
...................... 16
2.1.3
Putting the Bite on Metals
-
Chelation
..................... 17
2.1.4
Do I Look Big on That?
-
Chelate Ring Size
.................. 22
2.1.5
Different Tribes
-
Donor Group Variation
................... 23
2.1.6
Ligands with More Bite
-
Denticity
...................... 24
2.2
Monodentate
Ligands
-
The Simple Type
....................... 26
2.2.1
Basic Binders
................................. 26
2.2.2
Amines Ain t Ammines
-
Ligand Families
................... 27
2.2.3
Meeting More Metals
-
Bridging Ligands
................... 27
2.3
Greed is Good
-
Polydentate Ligands
......................... 29
2.3.1
The Simple Chelate
.............................. 29
2.3.2
More Teeth, Stronger Bite
-
Polydentates
................... 31
2.3.3
Many-Armed Monsters
-
Introducing Ligand Shape
.............. 32
2.4
Polynucleating Species
-
Molecular Bigamists
.................... 33
2.4.1
When One is Not Enough
........................... 33
2.4.2
Vive la Difference
-
Mixed-metal Complexation
................ 34
2.4.3
Supersized
-
Binding to Macromolecules
................... 36
2.5
A Separate Race
-
Organometallic Species
...................... 36
Concept Keys
.................................... 38
Further Reading
................................... 39
vi
Contents
3
Complexes
........................................ 41
3.1
The Central
Metal Ion
................................ 41
3.2
Metal-Ligand
Marriage
............................... 42
3.2.1
The Coordinate Bond.............................
42
3.2.2
The Foundation
of Coordination Chemistry
.................. 42
3.2.3
Complex Shape
-
Not Just Any Which Way
.................. 45
3.3
Holding On
-
The Nature of Bonding in Metal Complexes
............... 49
3.3.1
An Ionic Bonding Model
-
Introducing Crystal Field Theory
.......... 53
3.3.2
A Covalent Bonding Model
-
Embracing Molecular Orbital Theory
....... 57
3.3.3
Ligand Field Theory
-
Making Compromises
................. 62
3.3.4
Bonding Models Extended
.......................... 63
3.4
Coupling
-
Polymetallic Complexes
......................... 73
3.5
Making Choices
................................... 75
3.5.1
Selectivity
-
Of all the Molecules in all the World, Why This One?
....... 75
3.5.2
Preferences
-
Do You Like What I Like?
.................... 75
3.5.3
Complex Lifetimes
-
Together, Forever?
.................... 77
3.6
Complexation Consequences
............................. 80
Concept Keys
.................................... 81
Further Reading
................................... 82
4
Shape
.......................................... 83
4.1
Getting in Shape
................................... 83
4.2
Forms of Complex Life
-
Coordination Number and Shape
.............. 86
4.2.1
One Coordination (ML)
............................ 86
4.2.2
Two Coordination (ML2)
........................... 87
4.2.3
Three Coordination (ML3)
.......................... 88
4.2.4
Four Coordination (ML4)
........................... 89
4.2.5
Five Coordination (ML5)
........................... 93
4.2.6
Six Coordination (ML6)
............................ 96
4.2.7
Higher Coordination Numbers (ML7 to ML9)
................. 98
4.3
Influencing Shape
.................................. 101
4.3.1
Metallic Genetics
-
Metal Ion Influences
.................... 101
4.3.2
Moulding a Relationship
-
Ligand Influences
................. 103
4.3.3
Chameleon Complexes
............................ 105
4.4
Isomerism
-
Real
3D
Effects
............................. 105
4.4.1
Introducing Stereoisomers
........................... 106
4.4.2
Constitutional (Structural) Isomerism
..................... 106
4.4.3
Stereoisomerism: in Place
-
Positional Isomers; in Space
-
Optical Isomers
... 109
4.4.4
What s Best?
- Isomer
Preferences
...................... 1
13
4.5
Sophisticated Shapes
................................. 115
4.5.1
Compounds of Polydentate Ligands
...................... 46
4.5.2
Encapsulation Compounds
.......................... 11^
4.5.3
Host-Guest Molecular Assemblies
...................... 121
4.6
Defining Shape
................................... 123
Concept Keys
.................................... 123
Further Reading
................................... 124
Contents
vii
5
Stability
......................................... 125
5.1
The Makings of a Stable Relationship
......................... 125
5.1.1
Bedded Down
-
Thermodynamic Stability
................... 125
5.1.2
Factors Influencing Stability of Metal Complexes
............... 127
5.1.3
Overall Stability Constants
.......................... 138
5.1.4
Undergoing Change
-
Kinetic Stability
.................... 141
5.2
Complexation
-
Will It Last?
............................. 143
5.2.1
Thermodynamic and Kinetic Stability
..................... 143
5.2.2
Kinetic Rate Constants
............................ 144
5.2.3
Lability and Inertness in Octahedral Complexes
................ 145
5.3
Reactions
...................................... 146
5.3.1
A New Partner
-
Substitution
......................... 147
5.3.2
A New Body
-
Stereochemical Change
.................... 155
5.3.3
A New Face
-
Oxidation-Reduction
...................... 160
5.3.4
A New Suit
-
Ligand-centred Reactions
.................... 169
Concept Keys
.................................... 170
Further Reading
................................... 170
6
Synthesis
......................................... 173
6.1
Molecular Creation
-
Ways to Make Complexes
.................... 173
6.2
Core Metal Chemistry
-
Periodic Table Influences
................... 173
6.2.1
s
Block: Alkali and Alkaline Earth Metals
................... 173
6.2.2
ρ
Block: Main Group Metals
......................... 174
6.2.3
d
Block: Transition Metals
.......................... 175
6.2.4
f
Block: Inner Transition Metals (Lanthanoids and Actinoids)
.......... 176
6.2.5
Beyond Natural Elements
........................... 178
6.3
Reactions Involving the Coordination Shell
...................... 179
6.3.1
Ligand Substitution Reactions in Aqueous Solution
............... 179
6.3.2
Substitution Reactions in Nonaqueous Solvents
................ 184
6.3.3
Substitution Reactions without using a Solvent
................. 186
6.3.4
Chiral Complexes
............................... 189
6.3.5
Catalysed Reactions
............................. 190
6.4
Reactions Involving the Metal Oxidation State
.................... 190
6.5
Reactions Involving Coordinated Ligands
....................... 194
6.5.1
Metal-directed Reactions
........................... 194
6.5.2
Reactions of Coordinated Ligands
....................... 197
6.6
Organometallic Synthesis
.............................. 203
Concept Keys
.................................... 206
Further Reading
................................... 207
7
Properties
........................................ 209
7.1
Finding Ways to Make Complexes Talk
-
Investigative Methods
............ 209
7.2
Getting Physical
-
Methods and Outcomes
...................... 210
7.3
Probing the Life of Complexes
-
Using Physical Methods
............... 214
7.3.1
Peak Performance
-
Illustrating Selected Physical Methods
........... 216
7.3.2
Pretty in Red?
-
Colour and the Spectrochemical Series
............ 220
viii Contents
7.3.3
A Magnetic Personality?
-
Paramagnetism and Diamagnetism
......... 223
7.3.4
Ligand Field Stabilization
........................... 225
Concept Keys
.................................... 227
Further Reading
................................... 227
8
A Complex Life
..................................... 229
8.1
Life s a Metal Ion
.................................. 229
8.1.1
Biological Ligands
.............................. 229
8.1.2
Metal Ions in Biology
............................. 231
8.1.3
Classes of Metallobiomolecules
........................ 233
8.2
Metalloproteins
and Metalloenzymes
......................... 233
8.2.1
Iron-containing Biomolecules
......................... 234
8.2.2
Copper-containing Biomolecules
....................... 240
8.2.3
Zinc-containing Biomolecules
......................... 242
8.2.4
Other Metal-containing Biomolecules
..................... 243
8.2.5
Mixed-Metal Proteins
............................. 244
8.3
Doing What Comes Unnaturally
-
Synthetic Biomolecules
............... 245
8.4
A Laboratory-free Approach
-
In Silico Prediction
................... 247
Concept Keys
.................................... 249
Further Reading
................................... 250
9
Complexes and Commerce
................................ 251
9.1
Kill or Cure?
-
Complexes as Drugs
......................... 251
9.1.1
Introducing Metallodrugs
........................... 252
9.1.2
Anticancer
Drugs
............................... 252
9.1.3
Other Metallodrugs
.............................. 255
9.2
How Much?
-
Analysing with Complexes
....................... 256
9.2.1
Fluoroimmunoassay
............................. 256
9.2.2
Fluoroionophores
............................... 258
9.3
Profiting from Complexation
............................. 259
9.3.1
Metal Extraction
............................... 259
9.3.2
Industrial Roles for Ligands and Coordination Complexes
........... 261
9.4
Being Green
..................................... 263
9.4.1
Complexation in Remediation
......................... 264
9.4.2
Better Ways to Synthesize Fine Organic Chemicals
............... 264
9.5
Complex Futures
................................... 264
9.5.1
Taking Stock
................................. 265
9.5.2
Crystal Ball Gazing
.............................. 265
Concept Keys
.................................... 266
Further Reading
................................... 266
Appendix A: Nomenclature
.................................. 269
Appendix B: Molecular Symmetry: The Point Group
..................... 277
Index
............................................. 283
INTRODUCTION
TO
COORDINATION
CHEMISTRY
■ GEOFFREY A. LAWRANCE, University of Newcastle, Callaghan, Australia
At the heart of coordination chemistry lies the coordinate bond, in its simplest sense arising from
donation of a pair of electrons from a donor atom to an empty orbital on a central metalloid or
metal. Metals overwhelmingly exist as their cations, but these are rarely met naked
-
they are
clothed in an array of other atoms, molecules or ions that involve coordinate covalent bonds
(hence the name coordination compounds). These metal ion complexes are ubiquitous in nature,
and are central to an array of natural and synthetic reactions.
Written in a highly readable, descriptive and accessible style Introduction to Coordination Chemistry
describes properties of coordination compounds such as colour, magnetism and reactivity as well as
the logic in their assembly and nomenclature. It is illustrated with many examples of the importance
of coordination chemistry in real life, and includes extensive references and a bibliography.
Introduction to Coordination Chemistry is a comprehensive and insightful discussion of one of the
primary fields of study in Inorganic Chemistry for both undergraduate and non-specialist readers.
ADVANCED TEXTBOOK
This series reflects the pivotal role of modern inorganic and physical chemistry in a whole range of
emerging areas, such as materials chemistry, green chemistry and bioinorganic chemistry, as well as
providing a solid grounding in established areas such as solid state chemistry, coordination chemistry,
main group chemistry and physical inorganic chemistry.
Enjoyed this book?
Why not tell others about it
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ISBN
978-0-470-51931-8
8047 0я
519318
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| illustrated | Illustrated |
| indexdate | 2024-07-09T22:04:56Z |
| institution | BVB |
| isbn | 9780470519318 9780470519301 |
| language | English |
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| spelling | Lawrance, Geoffrey A. Verfasser aut Introduction to coordination chemistry Geoffrey A. Lawrance 1. publ. Chichester Wiley 2010 XIII, 290 S. Ill., graph. Darst. txt rdacontent n rdamedia nc rdacarrier A Wiley textbook series Inorganic chemistry Coordination compounds Koordinationslehre (DE-588)4133952-6 gnd rswk-swf Komplexe (DE-588)4133953-8 gnd rswk-swf Koordinationslehre (DE-588)4133952-6 s DE-604 Komplexe (DE-588)4133953-8 s Digitalisierung UB Bayreuth application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=018662018&sequence=000003&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA Inhaltsverzeichnis Digitalisierung UB Bayreuth application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=018662018&sequence=000004&line_number=0002&func_code=DB_RECORDS&service_type=MEDIA Klappentext |
| spellingShingle | Lawrance, Geoffrey A. Introduction to coordination chemistry Coordination compounds Koordinationslehre (DE-588)4133952-6 gnd Komplexe (DE-588)4133953-8 gnd |
| subject_GND | (DE-588)4133952-6 (DE-588)4133953-8 |
| title | Introduction to coordination chemistry |
| title_auth | Introduction to coordination chemistry |
| title_exact_search | Introduction to coordination chemistry |
| title_full | Introduction to coordination chemistry Geoffrey A. Lawrance |
| title_fullStr | Introduction to coordination chemistry Geoffrey A. Lawrance |
| title_full_unstemmed | Introduction to coordination chemistry Geoffrey A. Lawrance |
| title_short | Introduction to coordination chemistry |
| title_sort | introduction to coordination chemistry |
| topic | Coordination compounds Koordinationslehre (DE-588)4133952-6 gnd Komplexe (DE-588)4133953-8 gnd |
| topic_facet | Coordination compounds Koordinationslehre Komplexe |
| url | http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=018662018&sequence=000003&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=018662018&sequence=000004&line_number=0002&func_code=DB_RECORDS&service_type=MEDIA |
| work_keys_str_mv | AT lawrancegeoffreya introductiontocoordinationchemistry |