Advanced structural inorganic chemistry:
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| Sprache: | English |
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Oxford
Oxford Univ. Press
2008
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| Ausgabe: | 1. publ. |
| Schriftenreihe: | International Union of Crystallography texts on crystallography
10 |
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| Online-Zugang: | Inhaltsverzeichnis |
| Beschreibung: | Hier auch später erschienene, unveränderte Nachdrucke |
| Beschreibung: | XX, 819 S. Ill., graph. Darst. |
| ISBN: | 9780199216949 9780199216956 |
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| 100 | 1 | |a Li, Wai-Kee |e Verfasser |0 (DE-588)1028491433 |4 aut | |
| 245 | 1 | 0 | |a Advanced structural inorganic chemistry |c Wai-Kee Li ; Gong-Du Zhou ; Thomas Chung Wai Mak |
| 250 | |a 1. publ. | ||
| 264 | 1 | |a Oxford |b Oxford Univ. Press |c 2008 | |
| 300 | |a XX, 819 S. |b Ill., graph. Darst. | ||
| 336 | |b txt |2 rdacontent | ||
| 337 | |b n |2 rdamedia | ||
| 338 | |b nc |2 rdacarrier | ||
| 490 | 1 | |a International Union of Crystallography texts on crystallography |v 10 | |
| 500 | |a Hier auch später erschienene, unveränderte Nachdrucke | ||
| 650 | 4 | |a Chemistry, Inorganic | |
| 650 | 4 | |a Chemistry, Physical and theoretical | |
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| 689 | 0 | |5 DE-604 | |
| 700 | 1 | |a Zhou, Gong-Du |e Verfasser |4 aut | |
| 700 | 1 | |a Mak, Thomas C. |d 1936- |e Verfasser |0 (DE-588)17224661X |4 aut | |
| 830 | 0 | |a International Union of Crystallography texts on crystallography |v 10 |w (DE-604)BV002805877 |9 10 | |
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Datensatz im Suchindex
| _version_ | 1804137506957950976 |
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| adam_text | Contents
List of Contributors xxi
Part I Fundamentals of Bonding Theory 1
1 Introduction to Quantum Theory 3
1.1 Dual nature of light and matter 4
1.2 Uncertainty principle and probability concept 5
1.3 Electronic wavefunction and probability density function 6
1.4 Electronic wave equation: the Schrödinger equation 10
1.5 Simple applications of the Schrödinger equation 13
1.5.1 Particle in a one-dimensional box 13
1.5.2 Particle in a three-dimensional box 17
1.5.3 Particle in a ring 21
1.5.4 Particle in a triangle 23
References 28
2 The Electronic Structure of Atoms 29
2.1 The Hydrogen Atom 29
2.1.1 Schrödinger equation for the hydrogen atom 29
2.1.2 Angular functions of the hydrogen atom 31
2.1.3 Radial functions and total wavefunctions of the
hydrogen atom 34
2.1.4 Relative sizes of hydrogenic Orbitals and the probability
criterion 38
2.1.5 Energy levels of hydrogenic orbitals; summary 42
2.2 The helium atom and the Pauli exclusion principle 42
2.2.1 The helium atom: ground State 43
2.2.2 Determinantal wavefunction and the Pauli Exclusion
Principle 48
2.2.3 The helium atom: the ls12s1 configuration 51
2.3 Many-electron atoms: electronic configuration and spectroscopic
terms 54
2.3.1 Many-electron atoms 54
2.3.2 Ground electronic configuration for many-electron atoms 55
2.3.3 Spectroscopic terms arising from a given electronic
configuration 56
2.3.4 Hund s rules on spectroscopic terms 60
2.3.5 j-j Coupling 62
2.4 Atomic properties 64
2.4.1 Ionization energy and electron affinity 64
Contents
2.4.2 Electronegativity: the spectroscopic scale 67
2.4.3 Relativistic effects on the properties of the elements 71
References 76
Covalent Bonding in Molecules 77
3.1 The hydrogen molecular ion: bonding and antibonding molecular
Orbitals 77
3.1.1 The variational method 77
3.1.2 The hydrogen molecular ion: energy consideration 79
3.1.3 The hydrogen molecular ion: wavefunctions 82
3.1.4 Essentials of molecular orbital theory 84
3.2 The hydrogen molecule: molecular orbital and valence bond
treatments 85
3.2.1 Molecular orbital theory for H2 85
3.2.2 Valence bond treatment of H2 86
3.2.3 Equivalence of the molecular orbital and valence
bond modeis 89
3.3 Diatomic molecules 91
3.3.1 Homonuclear diatomic molecules 92
3.3.2 Heteronuclear diatomic molecules 96
3.4 Linear triatomic molecules and sp hybridization schemes 99
3.4.1 Beryllium hydride, BeH2 99
3.4.2 Hybridization scheme for linear triatomic molecules 100
3.4.3 Carbon dioxide, CO2 101
3.4.4 The sp (n = 1-3) hybrid Orbitals 104
3.4.5 Covalent radii 109
3.5 Hückel molecular orbital theory for conjugated polyenes 110
3.5.1 Hückel molecular orbital theory and its application to
ethylene and butadiene 110
3.5.2 Predicting the course of a reaction by considering the
symmetry of the w avefunction 113
References 116
Chemical Bonding in Condensed Phases 11 s
4.1 Chemical classification of solids 118
4.2 Ionicbond 121
4.2.1 Ionic size: crystal radii of ions 121
4.2.2 Lattice energies of ionic compounds 124
4.2.3 Ionic liquids 126
4.3 Metallic bonding and band theory 128
4.3.1 Chemical approach based on molecular orbital theory 128
4.3.2 Semiconductors 130
4.3.3 Variation of structure types of 4d and 5d transition metals 131
4.3.4 Metallic radii 132
4.3.5 Melting and boiling points and Standard enthalpies of
atomization of the metallic elements 133
Contents
XI
4.4 Van der Waals interactions 134
4.4.1 Physical origins of van der Waals interactions 135
4.4.2 Intermolecular potentials and van der Waals radii 138
References 139
5 Computational Chemistry 140
5.1 Introduction 140
5.2 Semi-empirical and ab initio methods 141
5.3 Basis sets 142
5.3.1 Minimal basis set 142
5.3.2 Double zeta and split valence basis sets 143
5.3.3 Polarization functions and diffuse functions 143
5.4 Electron correlation 144
5.4.1 Configuration interaction 145
5.4.2 Perturbation methods 146
5.4.3 Coupled-cluster and quadratic configuration interaction
methods 146
5.5 Density functional theory 147
5.6 Performance of theoretical methods 148
5.7 Composite methods 151
5.8 Illustrative examples 152
5.8.1 A stable argon compound: HArF 152
5.8.2 An all-metal aromatic species: Al^ 154
5.8.3 Anovel pentanitrogen cation: Nj 156
5.8.4 Linear triatomics with noble gas-metal bonds 158
5.9 Software packages 162
References 163
Part II Symmetry in Chemistry 165
6 Symmetry and Elements of Group Theory 167
6.1 Symmetry elements and symmetry operations 167
6.1.1 Proper rotation axis Cn 167
6.1.2 Symmetry plane a 168
6.1.3 Inversion center i 169
6.1.4 Improper rotation axis Sn 169
6.1.5 Identity element E 170
6.2 Molecular point groups 170
6.2.1 Classification of point groups 170
6.2.2 Identifying point groups 178
6.2.3 Dipole moment and optical activity 179
6.3 Character tables 180
6.4 The direct product and its use 185
6.4.1 The direct product 185
6.4.2 Identifying non-zero integrals and selection rules in
spectroscopy 187
6.4.3 Molecular term Symbols 189
References 193
Appendix 6.1 Character tables of point groups 195
Contents
Application of Group Theory to Molecular
Systems 213
7.1 Molecular orbital theory 213
7.1.1 AH„ (« = 2-6) molecules 214
7.1.2 Hückel theory for cyclic conjugated polyenes 221
7.1.3 Cyclic Systems involving d Orbitals 227
7.1.4 Linear combinations of ligand Orbitals for AL4 molecules
with r j symmetry 228
7.2 Construction of hybrid Orbitals 232
7.2.1 Hybridization schemes 232
7.2.2 Relationship between the coefficient matrices for the hybrid
and molecular orbital wavefunctions 233
7.2.3 Hybrids with d-orbital participation 234
7.3 Molecular vibrations 236
7.3.1 The symmetries and activities of the normal modes 236
7.3.2 Some illustrative examples 239
7.3.3 CO Stretch in metal carbonyl complexes 246
7.3.4 Linear molecules 252
7.3.5 Benzene and related molecules 254
References 259
8 Bonding in Coordination Compounds 261
8.1 Crystal field theory: d-orbital Splitting in octahedral and tetrahedral
complexes 261
8.2 Spectrochemical series, high spin and low spin complexes 263
8.3 Jahn-Teller distortion and other crystal fields 265
8.4 Octahedral crystal field Splitting of spectroscopic terms 267
8.5 Energy level diagrams for octahedral complexes 268
8.5.1 Orgel diagrams 268
8.5.2 Intensities and band widths of d-d spectral lines 271
8.5.3 Tanabe-Sugano diagrams 274
8.5.4 Electronic spectra of selected metal complexes 274
8.6 Correlation of weak and strong field approximations 279
8.7 Spin-orbit interaction in complexes: the double group 280
8.8 Molecular orbital theory for octahedral complexes 282
8.8.1 a bonding in octahedral complexes 283
8.8.2 Octahedral complexes with n bonding 285
8.8.3 The eighteen-electron rule 288
8.9 Electronic spectra of square planar complexes 289
8.9.1 Energy level scheme for square-planar complexes 289
8.9.2 Electronic spectra of square-planar halides and cyanides 291
8.10 Vibronic interaction in transition metal complexes 294
8.11 The 4f Orbitals and their crystal field Splitting patterns 295
8.11.1 The shapesof the 4f orbitals 295
8.11.2 Crystal field Splitting patterns of the 4f Orbitals 297
References 298
Contents xjjj
9 Symmetry in Crystals 300
9.1 The crystal as a geometrical entity 300
9.1.1 Interfacial angles 300
9.1.2 Miller indices 301
9.1.3 Thirty-two crystal classes (crystallographic point groups) 301
9.1.4 Stereographic projection 303
9.1.5 Acentric crystalline materials 304
9.2 The crystal as a lattice 307
9.2.1 The lattice concept 307
9.2.2 Unit cell 307
9.2.3 Fourteen Bravais lattices 309
9.2.4 Seven crystal Systems 309
9.2.5 Unit cell transformation 310
9.3 Space groups 312
9.3.1 Screw axes and glide planes 312
9.3.2 Graphic Symbols for symmetry elements 313
9.3.3 Hermann-Mauguin space-group symbols 316
9.3.4 International Tables for Crystallography 316
9.3.5 Coordinates of equipoints 317
9.3.6 Space group diagrams 320
9.3.7 Information on some commonly occurring space groups 323
9.3.8 Using the International Tables 323
9.4 Determination of space groups 323
9.4.1 Friedel s law 323
9.4.2 Laue classes 325
9.4.3 Deduction of lattice centering and translational symmetry
elements from systemic absences 328
9.5 Selected space groups and examples of crystal structures 333
9.5.1 Molecular symmetry and site symmetry 333
9.5.2 Symmetry deductions: assignment of atoms and groups to
equivalent positions 333
9.5.3 Racemic crystal and conglomerate 338
9.5.4 Occurrence of space groups in crystals 338
9.6 Application of space group symmetry in crystal structure
determination 339
9.6.1 Triclinic and monoclinic space groups 340
9.6.2 Orthorhombic space groups 343
9.6.3 Tetragonal space groups 345
9.6.4 Trigonal and rhombohedral space groups 347
9.6.5 Hexagonal space groups 350
9.6.6 Cubic space groups 353
References 362
10 Basic Inorganic Crystal Structures and
Materials 364
10.1 Cubic dosest packing and related structures 364
10.1.1 Cubic dosest packing (ccp) 364
Contents
10.1.2 Structure of NaCl and related compounds 366
10.1.3 Structure of CaF2 and related compounds 370
10.1.4 Structure of cubic zinc Sulfide 371
10.1.5 Structure of spinel and related compounds 373
10.2 Hexagonal dosest packing and related structures 375
10.2.1 Hexagonal closest packing (hcp) 375
10.2.2 Structure of hexagonal zinc sulfide 376
10.2.3 Structure of NiAs and related compounds 376
10.2.4 Structure of Cdl2 and related compounds 377
10.2.5 Structure ofa-Al2O3 379
10.2.6 Structure ofrutile 380
10.3 Body-centered cubic packing and related structures 381
10.3.1 Body-centered cubic packing (bcp) 381
10.3.2 Structure and properties ofa-Agl 383
10.3.3 Structure of CsCl and related compounds 384
10.4 Perovskite and related compounds 385
10.4.1 Structure of perovskite 385
10.4.2 Crystal structure of BaTiO3 388
10.4.3 Superconductors of perovskite structure type 389
10.4.4 ReC 3 and related compounds 390
10.5 Hard magnetic materials 391
10.5.1 Survey of magnetic materials 391
10.5.2 Structure ofSmCo5 and Sm2Co17 393
10.5.3 Structure ofNd2Fe14B 393
References 395
Part III Structural Chemistry of Selected Elements 397
11 Structural Chemistry of Hydrogen 399
11.1 The bonding types of hydrogen 399
11.2 Hydrogen bond 403
11.2.1 Nature and geometry of the hydrogen bond 403
11.2.2 The strength of hydrogen bonds 405
11.2.3 Symmetrical hydrogen bond 406
11.2.4 Hydrogen bonds in organometallic compounds 408
11.2.5 The universality and importance of hydrogen bonds 409
11.3 Non-conventional hydrogen bonds 411
11.3.1 X-H- •• n hydrogen bond 411
11.3.2 Transition metal hydrogen bond X-H-•• M 412
11.3.3 Dihydrogen bond X-H-•¦ H-E 413
11.3.4 Inverse hydrogen bond 415
11.4 Hydride complexes 416
11.4.1 Covalent metal hydride complexes 417
11.4.2 Interstitial and high-coordinate hydride complexes 419
11.5 Molecular hydrogen (H2) coordination compounds and r-bond
complexes 422
11.5.1 Structure and bonding of H2 coordination compounds 422
11.5.2 X-H (T-bond coordination metal complexes 424
Contents
xv
11.5.3 Agosticbond 425
11.5.4 Structure and bonding of a complexes 428
References 430
12 Structural Chemistry of Alkali and
Alkaline-Earth Metals 432
12.1 Survey of the alkali metals 432
12.2 Structure and bonding in inorganic alkali metal compounds 433
12.2.1 Alkali metal oxides 433
12.2.2 Lithium nitride 435
12.2.3 Inorganic alkali metal complexes 436
12.3 Structure and bonding in organic alkali metal compounds 442
12.3.1 Methyllithium and related compounds 442
12.3.2 n-Complexes oflithium 443
12.3.3 7r-Complexes of sodium and potassium 445
12.4 Alkalides and electrides 446
12.4.1 Alkalides 446
12.4.2 Electrides 447
12.5 Survey of the alkaline-earth metals 449
12.6 Structure of compounds of alkaline-earth metals 450
12.6.1 Group 2 metal complexes 450
12.6.2 Group 2 metal nitrides 451
12.6.3 Group 2 low-valent oxides and nitrides 452
12.7 Organometallic compounds of group 2 elements 454
12.7.1 Polymeric chains 454
12.7.2 Grignard reagents 454
12.7.3 Alkaline-earth metallocenes 455
12.8 Alkali and alkaline-earth metal complexes with inverse
crown structures 456
References 458
13 Structural Chemistry of Group 13 Elements 460
13.1 Survey of the group 13 elements 460
13.2 Elemental Boron 461
13.3 Borides 464
13.3.1 Metal borides 464
13.3.2 Non-metal borides 467
13.4 Boranes and carboranes 470
13.4.1 Molecular structure and bonding 470
13.4.2 Bond valence in molecular skeletons 472
13.4.3 Wade srules 473
13.4.4 Chemical bonding in c/ojo-boranes 475
13.4.5 Chemical bonding in nido- and arac/mo-boranes 477
13.4.6 Electron-counting scheme for macropolyhedral
boranes: mno rule 479
13.4.7 Electronic structure of /J-rhombohedral boron 481
13.4.8 Persubstifuted derivatives of icosahedral borane B^H^ 482
13.4.9 Boranes and carboranes as ligands 483
Contents
13.4.10 Carborane skeletons beyond the icosahedron 485
13.5 Boric acid and borates 486
13.5.1 Boric acid 486
13.5.2 Structureof borates 487
13.6 Organometallic compounds of group 13 elements 490
13.6.1 Compounds with bridged structure 490
13.6.2 Compounds with n bonding 491
13.6.3 Compounds containing M-M bonds 492
13.6.4 Linear catenation in heavier group 13 elements 494
13.7 Structure of naked anionic metalloid clusters 494
13.7.1 Structure ofGa84[N(SiMe3)2]2Ö 495
13.7.2 Structure ofNaTl 495
13.7.3 Naked Tl™~ anion clusters 496
References 498
14 Structural Chemistry of Group 14 Elements 500
14.1 Allotropic modifications of carbon 500
14.1.1 Diamond 500
14.1.2 Graphite 501
14.1.3 Fullerenes 502
14.1.4 Amorphous carbon 506
14.1.5 Carbon nanotubes 507
14.2 Compounds of carbon 509
14.2.1 Aliphatic compounds 509
14.2.2 Aromatic compounds 510
14.2.3 Fullerenic compounds 511
14.3 Bonding in carbon compounds 517
14.3.1 Types of bonds formed by the carbon atom 517
14.3.2 Coordination numbers of carbon 520
14.3.3 Bond lengthsof C-C and C-X bonds 520
14.3.4 Factors influencing bond lengths 520
14.3.5 Abnormal carbon-carbon single bonds 524
14.3.6 Complexes containing a naked carbon atom 527
14.3.7 Complexes containing naked dicarbon ligands 529
14.4 Structural chemistry of Silicon 533
14.4.1 Comparison of Silicon and carbon 533
14.4.2 Metal silicides 534
14.4.3 Stereochemistry of Silicon 535
14.4.4 Silicates 540
14.5 Structures of halides and oxides of heavier group 14 elements 544
14.5.1 Subvalent halides 544
14.5.2 Oxides of Ge, Sn, and Pb 546
14.6 Polyatomic anions of Ge, Sn, and Pb 547
14.7 Organometallic compounds of heavier group 14 elements 549
14.7.1 Cyclopentadienyl complexes 549
14.7.2 Sila- and germa-aromatic compounds 550
Contents
XVII
14.7.3 Cluster complexes of Ge, Sn, and Pb 551
14.7.4 Metalloid clusters of Sn 553
14.7.5 Donor-acceptor complexes of Ge, Sn and Pb 554
References 557
15 Structural Chemistry of Group 15 Elements 56i
15.1 The N2 molecule, all-nitrogen ions and dinitrogen complexes 561
15.1.1 The N2 molecule 561
15.1.2 Nitrogen ions and catenation of nitrogen 561
15.1.3 Dinitrogen complexes 564
15.2 Compounds of nitrogen 569
15.2.1 Molecular nitrogen oxides 569
15.2.2 Oxo-acids and oxo-ions of nitrogen 575
15.2.3 Nitrogen hydrides 578
15.3 Structure and bonding of elemental phosphorus and P„ groups 579
15.3.1 Elemental phosphorus 579
15.3.2 Polyphosphide anions 581
15.3.3 Structure of P„ groups in transition-metal complexes 581
15.3.4 Bond valence in P„ species 584
15.4 Bonding type and coordination geometry of phosphorus 586
15.4.1 Potential bonding types of phosphorus 586
15.4.2 Coordination geometries of phosphorus 587
15.5 Structure and bonding in phosphorus-nitrogen
and phosphorus-carbon compounds 590
15.5.1 Types ofP-Nbonds 590
15.5.2 Phosphazanes 591
15.5.3 Phosphazenes 593
15.5.4 Bonding types in phosphorus-carbon compounds 596
15.5.5 n -Coordination complexes of phosphorus-carbon
compounds 600
15.6 Structural chemistry of As, Sb, and Bi 602
15.6.1 Stereochemistry of As, Sb, and Bi 602
15.6.2 Metal-metal bonds and clusters 605
15.6.3 Intermolecular interactions in organoantimony and
organobismuth compounds 607
References 608
16 Structural Chemistry of Group 16 Elements 6io
16.1 Dioxygen and ozone 610
16.1.1 Structure and properties of dioxygen 610
16.1.2 Crystalline phases of solid oxygen 612
16.1.3 Dioxygen-related species and hydrogen peroxide 613
16.1.4 Ozone 614
16.2 Oxygen and dioxygen metal complexes 616
16.2.1 Coordination modes of oxygen in metal-oxo complexes 616
16.2.2 Ligation modes of dioxygen in metal complexes 616
16.2.3 Biological dioxygen carriers 618
Contents
16.3 Structure of water and ices 619
16.3.1 Water in the gas phase 620
16.3.2 Water in the solid phase: ices 620
16.3.3 Stractural model of liquid water 623
16.3.4 Protonated water species, H3O+ and H5O2 627
16.4 Allotropes of sulfur and polyatomic sulfur species 627
16.4.1 Allotropes of sulfur 626
16.4.2 Polyatomic sulfur ions 630
16.5 Sulfide anions as ligands in metal complexes 631
16.5.1 Monosulfide S2~ 631
16.5.2 DisulfideS^ 632
16.5.3 Polysulfides S^~ 632
16.6 Oxides and oxoacids of sulfur 634
16.6.1 Oxides of sulfur 634
16.6.2 Oxoacids of sulfur 637
16.7 Sulfur-nitrogen compounds 641
16.7.1 Tetrasulfur tetranitride, S4N4 641
16.7.2 S2N2 and (SN)* 642
16.7.3 Cyclic sulfur-nitrogen compounds 643
16.8 Structural chemistry of selenium and tellurium 644
16.8.1 Allotropes of selenium and tellurium 644
16.8.2 Polyatomic cations and anions of selenium and tellurium 644
16.8.3 Stereochemistry of selenium and tellurium 649
References 652
17 Structural Chemistry of Group 17 and
Group 18 Elements 654
17.1 Elemental halogens 654
17.1.1 Crystal structures of the elemental halogens 654
17.1.2 Homopolyatomic halogen anions 654
17.1.3 Homopolyatomic halogen cations 656
17.2 Interhalogen compounds and ions 657
17.2.1 Neutral interhalogen compounds 657
17.2.2 Interhalogen ions 659
17.3 Charge-transfer complexes of halogens 660
17.4 Halogen oxides and oxo compounds 662
17.4.1 Binary halogen oxides 662
17.4.2 Ternary halogen oxides 664
17.4.3 Halogen oxoacids and anions 666
17.4.4 Structural features of polycoordinate iodine compounds 668
17.5 Structural chemistry of noble gas compounds 670
17.5.1 General survey 670
17.5.2 Stereochemistry of xenon 671
17.5.3 Chemical bonding in xenon fluorides 672
17.5.4 Structures of some inorganic xenon compounds 674
17.5.5 Structures of some organoxenon compounds 677
Contents
XIX
17.5.6 Gold-xenon complexes 678
17.5.7 Krypton compounds 679
References 680
18 Structural Chemistry of Rare-Earth Elements 682
18.1 Chemistry of rare-earth metals 682
18.1.1 Trends in metallic and ionic radii: lanthanide contraction 682
18.1.2 Crystal structures of the rare-earth metals 683
18.1.3 Oxidation states 684
18.1.4 Term Symbols and electronic spectroscopy 685
18.1.5 Magnetic properties 687
18.2 Structure of oxides and halides of rare-earth elements 688
18.2.1 Oxides 688
18.2.2 Halides 689
18.3 Coordination geometry of rare-earth cations 690
18.4 Organometallic compounds of rare-earth elements 694
18.4.1 Cyclopentadienyl rare-earth complexes 694
18.4.2 Biscyclopentadienyl complexes 696
18.4.3 Benzene and cyclooctatetraenyl rare-earth complexes 697
18.4.4 Rare-earth complexes with other organic ligands 697
18.5 Reduction chemistry in oxidation State +2 699
18.5.1 Samarium(II) iodide 699
18.5.2 Decamethylsamarocene 700
References 701
19 Metal-Metal Bonds and Transition-Metal
Clusters 703
19.1 Bond valence and bond number of transition-metal clusters 703
19.2 Dinuclear complexes containing metal-metal bonds 705
19.2.1 Dinuclear transition-metal complexes conforming to the
18-electronrule 707
19.2.2 Quadruple bonds 708
19.2.3 Bond valence of metal-metal bond 711
19.2.4 Quintuple bonding in a dimetal complex 712
19.3 Clusters with three or four transition-metal atoms 713
19.3.1 Trinuclear clusters 713
19.3.2 Tetranuclear clusters 714
19.4 Clusters with more than four transition-metal atoms 715
19.4.1 Pentanuclear clusters 715
19.4.2 Hexanuclear clusters 715
19.4.3 Clusters with seven or more transition-metal atoms 717
19.4.4 Anionic carbonyl clusters with interstitial main-group atoms 718
19.5 Iso-bond valence and iso-structural series 719
19.6 Selected topics in metal-metal interactions 721
19.6.1 Aurophilicity 721
19.6.2 Argentophilicity and mixed metal complexes 724
Contents
19.6.3 Metal string molecules 724
19.6.4 Metal-based infinite chains and networks 729
References 731
20 Supramolecular Structural Chemistry 733
20.1 Introduction 733
20.1.1 Intermolecular interactions 733
20.1.2 Molecular recognition 734
20.1.3 Self-assembly 735
20.1.4 Crystal engineering 735
20.1.5 Supramolecular synthon 737
20.2 Hydrogen-bond directed assembly 738
20.2.1 Supramolecular architectures based on the carboxylic acid
dimer synthon 740
20.2.2 Graph-set encoding of hydrogen-bonding pattern 742
20.2.3 Supramolecular construction based on complementary
hydrogen bonding between heterocycles 744
20.2.4 Hydrogen-bonded networks exhibiting the supramolecular
rosette pattern 744
20.3 Supramolecular chemistry of the coordination bond 752
20.3.1 Principal types of supermolecules 752
20.3.2 Some examples of inorganic supermolecules 753
20.3.3 Synthetic strategies for inorganic supermolecules and
coordination polymers 757
20.3.4 Molecular polygons and tubes 760
20.3.5 Molecular polyhedra 762
20.4 Selected examples in crystal engineering 768
20.4.1 Diamondoid networks 768
20.4.2 Interlocked structures constructed from cucurbituril 772
20.4.3 Inorganic crystal engineering using hydrogen bonds 776
20.4.4 Generation and stabilization of unstable inorganic/organic
anions in urea/thiourea complexes 780
20.4.5 Supramolecular assembly of silver(I) polyhedra with
embedded acetylenediide dianion 784
20.4.6 Supramolecular assembly with the silver(I)-ethynide
synthon 792
20.4.7 Self-assembly of nanocapsules with pyrogallol[4]arene
macrocycles 797
20.4.8 Reticular design and synthesis of porous metal-organic
frameworks 799
20.4.9 One-pot synthesis of nanocontainer molecule 804
20.4.10 Filled carbon nanotubes 804
References 808
Index 8ii
|
| adam_txt |
Contents
List of Contributors xxi
Part I Fundamentals of Bonding Theory 1
1 Introduction to Quantum Theory 3
1.1 Dual nature of light and matter 4
1.2 Uncertainty principle and probability concept 5
1.3 Electronic wavefunction and probability density function 6
1.4 Electronic wave equation: the Schrödinger equation 10
1.5 Simple applications of the Schrödinger equation 13
1.5.1 Particle in a one-dimensional box 13
1.5.2 Particle in a three-dimensional box 17
1.5.3 Particle in a ring 21
1.5.4 Particle in a triangle 23
References 28
2 The Electronic Structure of Atoms 29
2.1 The Hydrogen Atom 29
2.1.1 Schrödinger equation for the hydrogen atom 29
2.1.2 Angular functions of the hydrogen atom 31
2.1.3 Radial functions and total wavefunctions of the
hydrogen atom 34
2.1.4 Relative sizes of hydrogenic Orbitals and the probability
criterion 38
2.1.5 Energy levels of hydrogenic orbitals; summary 42
2.2 The helium atom and the Pauli exclusion principle 42
2.2.1 The helium atom: ground State 43
2.2.2 Determinantal wavefunction and the Pauli Exclusion
Principle 48
2.2.3 The helium atom: the ls12s1 configuration 51
2.3 Many-electron atoms: electronic configuration and spectroscopic
terms 54
2.3.1 Many-electron atoms 54
2.3.2 Ground electronic configuration for many-electron atoms 55
2.3.3 Spectroscopic terms arising from a given electronic
configuration 56
2.3.4 Hund's rules on spectroscopic terms 60
2.3.5 j-j Coupling 62
2.4 Atomic properties 64
2.4.1 Ionization energy and electron affinity 64
Contents
2.4.2 Electronegativity: the spectroscopic scale 67
2.4.3 Relativistic effects on the properties of the elements 71
References 76
Covalent Bonding in Molecules 77
3.1 The hydrogen molecular ion: bonding and antibonding molecular
Orbitals 77
3.1.1 The variational method 77
3.1.2 The hydrogen molecular ion: energy consideration 79
3.1.3 The hydrogen molecular ion: wavefunctions 82
3.1.4 Essentials of molecular orbital theory 84
3.2 The hydrogen molecule: molecular orbital and valence bond
treatments 85
3.2.1 Molecular orbital theory for H2 85
3.2.2 Valence bond treatment of H2 86
3.2.3 Equivalence of the molecular orbital and valence
bond modeis 89
3.3 Diatomic molecules 91
3.3.1 Homonuclear diatomic molecules 92
3.3.2 Heteronuclear diatomic molecules 96
3.4 Linear triatomic molecules and sp" hybridization schemes 99
3.4.1 Beryllium hydride, BeH2 99
3.4.2 Hybridization scheme for linear triatomic molecules 100
3.4.3 Carbon dioxide, CO2 101
3.4.4 The sp" (n = 1-3) hybrid Orbitals 104
3.4.5 Covalent radii 109
3.5 Hückel molecular orbital theory for conjugated polyenes 110
3.5.1 Hückel molecular orbital theory and its application to
ethylene and butadiene 110
3.5.2 Predicting the course of a reaction by considering the
symmetry of the w avefunction 113
References 116
Chemical Bonding in Condensed Phases 11 s
4.1 Chemical classification of solids 118
4.2 Ionicbond 121
4.2.1 Ionic size: crystal radii of ions 121
4.2.2 Lattice energies of ionic compounds 124
4.2.3 Ionic liquids 126
4.3 Metallic bonding and band theory 128
4.3.1 Chemical approach based on molecular orbital theory 128
4.3.2 Semiconductors 130
4.3.3 Variation of structure types of 4d and 5d transition metals 131
4.3.4 Metallic radii 132
4.3.5 Melting and boiling points and Standard enthalpies of
atomization of the metallic elements 133
Contents
XI
4.4 Van der Waals interactions 134
4.4.1 Physical origins of van der Waals interactions 135
4.4.2 Intermolecular potentials and van der Waals radii 138
References 139
5 Computational Chemistry 140
5.1 Introduction 140
5.2 Semi-empirical and ab initio methods 141
5.3 Basis sets 142
5.3.1 Minimal basis set 142
5.3.2 Double zeta and split valence basis sets 143
5.3.3 Polarization functions and diffuse functions 143
5.4 Electron correlation 144
5.4.1 Configuration interaction 145
5.4.2 Perturbation methods 146
5.4.3 Coupled-cluster and quadratic configuration interaction
methods 146
5.5 Density functional theory 147
5.6 Performance of theoretical methods 148
5.7 Composite methods 151
5.8 Illustrative examples 152
5.8.1 A stable argon compound: HArF 152
5.8.2 An all-metal aromatic species: Al^ 154
5.8.3 Anovel pentanitrogen cation: Nj" 156
5.8.4 Linear triatomics with noble gas-metal bonds 158
5.9 Software packages 162
References 163
Part II Symmetry in Chemistry 165
6 Symmetry and Elements of Group Theory 167
6.1 Symmetry elements and symmetry operations 167
6.1.1 Proper rotation axis Cn 167
6.1.2 Symmetry plane a 168
6.1.3 Inversion center i 169
6.1.4 Improper rotation axis Sn 169
6.1.5 Identity element E 170
6.2 Molecular point groups 170
6.2.1 Classification of point groups 170
6.2.2 Identifying point groups 178
6.2.3 Dipole moment and optical activity 179
6.3 Character tables 180
6.4 The direct product and its use 185
6.4.1 The direct product 185
6.4.2 Identifying non-zero integrals and selection rules in
spectroscopy 187
6.4.3 Molecular term Symbols 189
References 193
Appendix 6.1 Character tables of point groups 195
Contents
Application of Group Theory to Molecular
Systems 213
7.1 Molecular orbital theory 213
7.1.1 AH„ (« = 2-6) molecules 214
7.1.2 Hückel theory for cyclic conjugated polyenes 221
7.1.3 Cyclic Systems involving d Orbitals 227
7.1.4 Linear combinations of ligand Orbitals for AL4 molecules
with r j symmetry 228
7.2 Construction of hybrid Orbitals 232
7.2.1 Hybridization schemes 232
7.2.2 Relationship between the coefficient matrices for the hybrid
and molecular orbital wavefunctions 233
7.2.3 Hybrids with d-orbital participation 234
7.3 Molecular vibrations 236
7.3.1 The symmetries and activities of the normal modes 236
7.3.2 Some illustrative examples 239
7.3.3 CO Stretch in metal carbonyl complexes 246
7.3.4 Linear molecules 252
7.3.5 Benzene and related molecules 254
References 259
8 Bonding in Coordination Compounds 261
8.1 Crystal field theory: d-orbital Splitting in octahedral and tetrahedral
complexes 261
8.2 Spectrochemical series, high spin and low spin complexes 263
8.3 Jahn-Teller distortion and other crystal fields 265
8.4 Octahedral crystal field Splitting of spectroscopic terms 267
8.5 Energy level diagrams for octahedral complexes 268
8.5.1 Orgel diagrams 268
8.5.2 Intensities and band widths of d-d spectral lines 271
8.5.3 Tanabe-Sugano diagrams 274
8.5.4 Electronic spectra of selected metal complexes 274
8.6 Correlation of weak and strong field approximations 279
8.7 Spin-orbit interaction in complexes: the double group 280
8.8 Molecular orbital theory for octahedral complexes 282
8.8.1 a bonding in octahedral complexes 283
8.8.2 Octahedral complexes with n bonding 285
8.8.3 The eighteen-electron rule 288
8.9 Electronic spectra of square planar complexes 289
8.9.1 Energy level scheme for square-planar complexes 289
8.9.2 Electronic spectra of square-planar halides and cyanides 291
8.10 Vibronic interaction in transition metal complexes 294
8.11 The 4f Orbitals and their crystal field Splitting patterns 295
8.11.1 The shapesof the 4f orbitals 295
8.11.2 Crystal field Splitting patterns of the 4f Orbitals 297
References 298
Contents xjjj
9 Symmetry in Crystals 300
9.1 The crystal as a geometrical entity 300
9.1.1 Interfacial angles 300
9.1.2 Miller indices 301
9.1.3 Thirty-two crystal classes (crystallographic point groups) 301
9.1.4 Stereographic projection 303
9.1.5 Acentric crystalline materials 304
9.2 The crystal as a lattice 307
9.2.1 The lattice concept 307
9.2.2 Unit cell 307
9.2.3 Fourteen Bravais lattices 309
9.2.4 Seven crystal Systems 309
9.2.5 Unit cell transformation 310
9.3 Space groups 312
9.3.1 Screw axes and glide planes 312
9.3.2 Graphic Symbols for symmetry elements 313
9.3.3 Hermann-Mauguin space-group symbols 316
9.3.4 International Tables for Crystallography 316
9.3.5 Coordinates of equipoints 317
9.3.6 Space group diagrams 320
9.3.7 Information on some commonly occurring space groups 323
9.3.8 Using the International Tables 323
9.4 Determination of space groups 323
9.4.1 Friedel's law 323
9.4.2 Laue classes 325
9.4.3 Deduction of lattice centering and translational symmetry
elements from systemic absences 328
9.5 Selected space groups and examples of crystal structures 333
9.5.1 Molecular symmetry and site symmetry 333
9.5.2 Symmetry deductions: assignment of atoms and groups to
equivalent positions 333
9.5.3 Racemic crystal and conglomerate 338
9.5.4 Occurrence of space groups in crystals 338
9.6 Application of space group symmetry in crystal structure
determination 339
9.6.1 Triclinic and monoclinic space groups 340
9.6.2 Orthorhombic space groups 343
9.6.3 Tetragonal space groups 345
9.6.4 Trigonal and rhombohedral space groups 347
9.6.5 Hexagonal space groups 350
9.6.6 Cubic space groups 353
References 362
10 Basic Inorganic Crystal Structures and
Materials 364
10.1 Cubic dosest packing and related structures 364
10.1.1 Cubic dosest packing (ccp) 364
Contents
10.1.2 Structure of NaCl and related compounds 366
10.1.3 Structure of CaF2 and related compounds 370
10.1.4 Structure of cubic zinc Sulfide 371
10.1.5 Structure of spinel and related compounds 373
10.2 Hexagonal dosest packing and related structures 375
10.2.1 Hexagonal closest packing (hcp) 375
10.2.2 Structure of hexagonal zinc sulfide 376
10.2.3 Structure of NiAs and related compounds 376
10.2.4 Structure of Cdl2 and related compounds 377
10.2.5 Structure ofa-Al2O3 379
10.2.6 Structure ofrutile 380
10.3 Body-centered cubic packing and related structures 381
10.3.1 Body-centered cubic packing (bcp) 381
10.3.2 Structure and properties ofa-Agl 383
10.3.3 Structure of CsCl and related compounds 384
10.4 Perovskite and related compounds 385
10.4.1 Structure of perovskite 385
10.4.2 Crystal structure of BaTiO3 388
10.4.3 Superconductors of perovskite structure type 389
10.4.4 ReC 3 and related compounds 390
10.5 Hard magnetic materials 391
10.5.1 Survey of magnetic materials 391
10.5.2 Structure ofSmCo5 and Sm2Co17 393
10.5.3 Structure ofNd2Fe14B 393
References 395
Part III Structural Chemistry of Selected Elements 397
11 Structural Chemistry of Hydrogen 399
11.1 The bonding types of hydrogen 399
11.2 Hydrogen bond 403
11.2.1 Nature and geometry of the hydrogen bond 403
11.2.2 The strength of hydrogen bonds 405
11.2.3 Symmetrical hydrogen bond 406
11.2.4 Hydrogen bonds in organometallic compounds 408
11.2.5 The universality and importance of hydrogen bonds 409
11.3 Non-conventional hydrogen bonds 411
11.3.1 X-H- •• n hydrogen bond 411
11.3.2 Transition metal hydrogen bond X-H-•• M 412
11.3.3 Dihydrogen bond X-H-•¦ H-E 413
11.3.4 Inverse hydrogen bond 415
11.4 Hydride complexes 416
11.4.1 Covalent metal hydride complexes 417
11.4.2 Interstitial and high-coordinate hydride complexes 419
11.5 Molecular hydrogen (H2) coordination compounds and r-bond
complexes 422
11.5.1 Structure and bonding of H2 coordination compounds 422
11.5.2 X-H (T-bond coordination metal complexes 424
Contents
xv
11.5.3 Agosticbond 425
11.5.4 Structure and bonding of a complexes 428
References 430
12 Structural Chemistry of Alkali and
Alkaline-Earth Metals 432
12.1 Survey of the alkali metals 432
12.2 Structure and bonding in inorganic alkali metal compounds 433
12.2.1 Alkali metal oxides 433
12.2.2 Lithium nitride 435
12.2.3 Inorganic alkali metal complexes 436
12.3 Structure and bonding in organic alkali metal compounds 442
12.3.1 Methyllithium and related compounds 442
12.3.2 n-Complexes oflithium 443
12.3.3 7r-Complexes of sodium and potassium 445
12.4 Alkalides and electrides 446
12.4.1 Alkalides 446
12.4.2 Electrides 447
12.5 Survey of the alkaline-earth metals 449
12.6 Structure of compounds of alkaline-earth metals 450
12.6.1 Group 2 metal complexes 450
12.6.2 Group 2 metal nitrides 451
12.6.3 Group 2 low-valent oxides and nitrides 452
12.7 Organometallic compounds of group 2 elements 454
12.7.1 Polymeric chains 454
12.7.2 Grignard reagents 454
12.7.3 Alkaline-earth metallocenes 455
12.8 Alkali and alkaline-earth metal complexes with inverse
crown structures 456
References 458
13 Structural Chemistry of Group 13 Elements 460
13.1 Survey of the group 13 elements 460
13.2 Elemental Boron 461
13.3 Borides 464
13.3.1 Metal borides 464
13.3.2 Non-metal borides 467
13.4 Boranes and carboranes 470
13.4.1 Molecular structure and bonding 470
13.4.2 Bond valence in molecular skeletons 472
13.4.3 Wade'srules 473
13.4.4 Chemical bonding in c/ojo-boranes 475
13.4.5 Chemical bonding in nido- and arac/mo-boranes 477
13.4.6 Electron-counting scheme for macropolyhedral
boranes: mno rule 479
13.4.7 Electronic structure of /J-rhombohedral boron 481
13.4.8 Persubstifuted derivatives of icosahedral borane B^H^" 482
13.4.9 Boranes and carboranes as ligands 483
Contents
13.4.10 Carborane skeletons beyond the icosahedron 485
13.5 Boric acid and borates 486
13.5.1 Boric acid 486
13.5.2 Structureof borates 487
13.6 Organometallic compounds of group 13 elements 490
13.6.1 Compounds with bridged structure 490
13.6.2 Compounds with n bonding 491
13.6.3 Compounds containing M-M bonds 492
13.6.4 Linear catenation in heavier group 13 elements 494
13.7 Structure of naked anionic metalloid clusters 494
13.7.1 Structure ofGa84[N(SiMe3)2]2Ö 495
13.7.2 Structure ofNaTl 495
13.7.3 Naked Tl™~ anion clusters 496
References 498
14 Structural Chemistry of Group 14 Elements 500
14.1 Allotropic modifications of carbon 500
14.1.1 Diamond 500
14.1.2 Graphite 501
14.1.3 Fullerenes 502
14.1.4 Amorphous carbon 506
14.1.5 Carbon nanotubes 507
14.2 Compounds of carbon 509
14.2.1 Aliphatic compounds 509
14.2.2 Aromatic compounds 510
14.2.3 Fullerenic compounds 511
14.3 Bonding in carbon compounds 517
14.3.1 Types of bonds formed by the carbon atom 517
14.3.2 Coordination numbers of carbon 520
14.3.3 Bond lengthsof C-C and C-X bonds 520
14.3.4 Factors influencing bond lengths 520
14.3.5 Abnormal carbon-carbon single bonds 524
14.3.6 Complexes containing a naked carbon atom 527
14.3.7 Complexes containing naked dicarbon ligands 529
14.4 Structural chemistry of Silicon 533
14.4.1 Comparison of Silicon and carbon 533
14.4.2 Metal silicides 534
14.4.3 Stereochemistry of Silicon 535
14.4.4 Silicates 540
14.5 Structures of halides and oxides of heavier group 14 elements 544
14.5.1 Subvalent halides 544
14.5.2 Oxides of Ge, Sn, and Pb 546
14.6 Polyatomic anions of Ge, Sn, and Pb 547
14.7 Organometallic compounds of heavier group 14 elements 549
14.7.1 Cyclopentadienyl complexes 549
14.7.2 Sila- and germa-aromatic compounds 550
Contents
XVII
14.7.3 Cluster complexes of Ge, Sn, and Pb 551
14.7.4 Metalloid clusters of Sn 553
14.7.5 Donor-acceptor complexes of Ge, Sn and Pb 554
References 557
15 Structural Chemistry of Group 15 Elements 56i
15.1 The N2 molecule, all-nitrogen ions and dinitrogen complexes 561
15.1.1 The N2 molecule 561
15.1.2 Nitrogen ions and catenation of nitrogen 561
15.1.3 Dinitrogen complexes 564
15.2 Compounds of nitrogen 569
15.2.1 Molecular nitrogen oxides 569
15.2.2 Oxo-acids and oxo-ions of nitrogen 575
15.2.3 Nitrogen hydrides 578
15.3 Structure and bonding of elemental phosphorus and P„ groups 579
15.3.1 Elemental phosphorus 579
15.3.2 Polyphosphide anions 581
15.3.3 Structure of P„ groups in transition-metal complexes 581
15.3.4 Bond valence in P„ species 584
15.4 Bonding type and coordination geometry of phosphorus 586
15.4.1 Potential bonding types of phosphorus 586
15.4.2 Coordination geometries of phosphorus 587
15.5 Structure and bonding in phosphorus-nitrogen
and phosphorus-carbon compounds 590
15.5.1 Types ofP-Nbonds 590
15.5.2 Phosphazanes 591
15.5.3 Phosphazenes 593
15.5.4 Bonding types in phosphorus-carbon compounds 596
15.5.5 n -Coordination complexes of phosphorus-carbon
compounds 600
15.6 Structural chemistry of As, Sb, and Bi 602
15.6.1 Stereochemistry of As, Sb, and Bi 602
15.6.2 Metal-metal bonds and clusters 605
15.6.3 Intermolecular interactions in organoantimony and
organobismuth compounds 607
References 608
16 Structural Chemistry of Group 16 Elements 6io
16.1 Dioxygen and ozone 610
16.1.1 Structure and properties of dioxygen 610
16.1.2 Crystalline phases of solid oxygen 612
16.1.3 Dioxygen-related species and hydrogen peroxide 613
16.1.4 Ozone 614
16.2 Oxygen and dioxygen metal complexes 616
16.2.1 Coordination modes of oxygen in metal-oxo complexes 616
16.2.2 Ligation modes of dioxygen in metal complexes 616
16.2.3 Biological dioxygen carriers 618
Contents
16.3 Structure of water and ices 619
16.3.1 Water in the gas phase 620
16.3.2 Water in the solid phase: ices 620
16.3.3 Stractural model of liquid water 623
16.3.4 Protonated water species, H3O+ and H5O2" 627
16.4 Allotropes of sulfur and polyatomic sulfur species 627
16.4.1 Allotropes of sulfur 626
16.4.2 Polyatomic sulfur ions 630
16.5 Sulfide anions as ligands in metal complexes 631
16.5.1 Monosulfide S2~ 631
16.5.2 DisulfideS^ 632
16.5.3 Polysulfides S^~ 632
16.6 Oxides and oxoacids of sulfur 634
16.6.1 Oxides of sulfur 634
16.6.2 Oxoacids of sulfur 637
16.7 Sulfur-nitrogen compounds 641
16.7.1 Tetrasulfur tetranitride, S4N4 641
16.7.2 S2N2 and (SN)* 642
16.7.3 Cyclic sulfur-nitrogen compounds 643
16.8 Structural chemistry of selenium and tellurium 644
16.8.1 Allotropes of selenium and tellurium 644
16.8.2 Polyatomic cations and anions of selenium and tellurium 644
16.8.3 Stereochemistry of selenium and tellurium 649
References 652
17 Structural Chemistry of Group 17 and
Group 18 Elements 654
17.1 Elemental halogens 654
17.1.1 Crystal structures of the elemental halogens 654
17.1.2 Homopolyatomic halogen anions 654
17.1.3 Homopolyatomic halogen cations 656
17.2 Interhalogen compounds and ions 657
17.2.1 Neutral interhalogen compounds 657
17.2.2 Interhalogen ions 659
17.3 Charge-transfer complexes of halogens 660
17.4 Halogen oxides and oxo compounds 662
17.4.1 Binary halogen oxides 662
17.4.2 Ternary halogen oxides 664
17.4.3 Halogen oxoacids and anions 666
17.4.4 Structural features of polycoordinate iodine compounds 668
17.5 Structural chemistry of noble gas compounds 670
17.5.1 General survey 670
17.5.2 Stereochemistry of xenon 671
17.5.3 Chemical bonding in xenon fluorides 672
17.5.4 Structures of some inorganic xenon compounds 674
17.5.5 Structures of some organoxenon compounds 677
Contents
XIX
17.5.6 Gold-xenon complexes 678
17.5.7 Krypton compounds 679
References 680
18 Structural Chemistry of Rare-Earth Elements 682
18.1 Chemistry of rare-earth metals 682
18.1.1 Trends in metallic and ionic radii: lanthanide contraction 682
18.1.2 Crystal structures of the rare-earth metals 683
18.1.3 Oxidation states 684
18.1.4 Term Symbols and electronic spectroscopy 685
18.1.5 Magnetic properties 687
18.2 Structure of oxides and halides of rare-earth elements 688
18.2.1 Oxides 688
18.2.2 Halides 689
18.3 Coordination geometry of rare-earth cations 690
18.4 Organometallic compounds of rare-earth elements 694
18.4.1 Cyclopentadienyl rare-earth complexes 694
18.4.2 Biscyclopentadienyl complexes 696
18.4.3 Benzene and cyclooctatetraenyl rare-earth complexes 697
18.4.4 Rare-earth complexes with other organic ligands 697
18.5 Reduction chemistry in oxidation State +2 699
18.5.1 Samarium(II) iodide 699
18.5.2 Decamethylsamarocene 700
References 701
19 Metal-Metal Bonds and Transition-Metal
Clusters 703
19.1 Bond valence and bond number of transition-metal clusters 703
19.2 Dinuclear complexes containing metal-metal bonds 705
19.2.1 Dinuclear transition-metal complexes conforming to the
18-electronrule 707
19.2.2 Quadruple bonds 708
19.2.3 Bond valence of metal-metal bond 711
19.2.4 Quintuple bonding in a dimetal complex 712
19.3 Clusters with three or four transition-metal atoms 713
19.3.1 Trinuclear clusters 713
19.3.2 Tetranuclear clusters 714
19.4 Clusters with more than four transition-metal atoms 715
19.4.1 Pentanuclear clusters 715
19.4.2 Hexanuclear clusters 715
19.4.3 Clusters with seven or more transition-metal atoms 717
19.4.4 Anionic carbonyl clusters with interstitial main-group atoms 718
19.5 Iso-bond valence and iso-structural series 719
19.6 Selected topics in metal-metal interactions 721
19.6.1 Aurophilicity 721
19.6.2 Argentophilicity and mixed metal complexes 724
Contents
19.6.3 Metal string molecules 724
19.6.4 Metal-based infinite chains and networks 729
References 731
20 Supramolecular Structural Chemistry 733
20.1 Introduction 733
20.1.1 Intermolecular interactions 733
20.1.2 Molecular recognition 734
20.1.3 Self-assembly 735
20.1.4 Crystal engineering 735
20.1.5 Supramolecular synthon 737
20.2 Hydrogen-bond directed assembly 738
20.2.1 Supramolecular architectures based on the carboxylic acid
dimer synthon 740
20.2.2 Graph-set encoding of hydrogen-bonding pattern 742
20.2.3 Supramolecular construction based on complementary
hydrogen bonding between heterocycles 744
20.2.4 Hydrogen-bonded networks exhibiting the supramolecular
rosette pattern 744
20.3 Supramolecular chemistry of the coordination bond 752
20.3.1 Principal types of supermolecules 752
20.3.2 Some examples of inorganic supermolecules 753
20.3.3 Synthetic strategies for inorganic supermolecules and
coordination polymers 757
20.3.4 Molecular polygons and tubes 760
20.3.5 Molecular polyhedra 762
20.4 Selected examples in crystal engineering 768
20.4.1 Diamondoid networks 768
20.4.2 Interlocked structures constructed from cucurbituril 772
20.4.3 Inorganic crystal engineering using hydrogen bonds 776
20.4.4 Generation and stabilization of unstable inorganic/organic
anions in urea/thiourea complexes 780
20.4.5 Supramolecular assembly of silver(I) polyhedra with
embedded acetylenediide dianion 784
20.4.6 Supramolecular assembly with the silver(I)-ethynide
synthon 792
20.4.7 Self-assembly of nanocapsules with pyrogallol[4]arene
macrocycles 797
20.4.8 Reticular design and synthesis of porous metal-organic
frameworks 799
20.4.9 One-pot synthesis of nanocontainer molecule 804
20.4.10 Filled carbon nanotubes 804
References 808
Index 8ii |
| any_adam_object | 1 |
| any_adam_object_boolean | 1 |
| author | Li, Wai-Kee Zhou, Gong-Du Mak, Thomas C. 1936- |
| author_GND | (DE-588)1028491433 (DE-588)17224661X |
| author_facet | Li, Wai-Kee Zhou, Gong-Du Mak, Thomas C. 1936- |
| author_role | aut aut aut |
| author_sort | Li, Wai-Kee |
| author_variant | w k l wkl g d z gdz t c m tc tcm |
| building | Verbundindex |
| bvnumber | BV023220125 |
| callnumber-first | Q - Science |
| callnumber-label | QD475 |
| callnumber-raw | QD475 |
| callnumber-search | QD475 |
| callnumber-sort | QD 3475 |
| callnumber-subject | QD - Chemistry |
| classification_rvk | VH 5800 VH 7900 |
| classification_tum | CHE 312f |
| ctrlnum | (OCoLC)890547051 (DE-599)GBV539629251 |
| dewey-full | 541.2 |
| dewey-hundreds | 500 - Natural sciences and mathematics |
| dewey-ones | 541 - Physical chemistry |
| dewey-raw | 541.2 |
| dewey-search | 541.2 |
| dewey-sort | 3541.2 |
| dewey-tens | 540 - Chemistry and allied sciences |
| discipline | Chemie / Pharmazie Chemie |
| discipline_str_mv | Chemie / Pharmazie Chemie |
| edition | 1. publ. |
| format | Book |
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| genre | (DE-588)4173536-5 Patentschrift gnd-content |
| genre_facet | Patentschrift |
| id | DE-604.BV023220125 |
| illustrated | Illustrated |
| index_date | 2024-07-02T20:15:40Z |
| indexdate | 2024-07-09T21:13:23Z |
| institution | BVB |
| isbn | 9780199216949 9780199216956 |
| language | English |
| oai_aleph_id | oai:aleph.bib-bvb.de:BVB01-016406040 |
| oclc_num | 890547051 |
| open_access_boolean | |
| owner | DE-703 DE-634 DE-91G DE-BY-TUM DE-19 DE-BY-UBM DE-11 DE-20 |
| owner_facet | DE-703 DE-634 DE-91G DE-BY-TUM DE-19 DE-BY-UBM DE-11 DE-20 |
| physical | XX, 819 S. Ill., graph. Darst. |
| publishDate | 2008 |
| publishDateSearch | 2008 |
| publishDateSort | 2008 |
| publisher | Oxford Univ. Press |
| record_format | marc |
| series | International Union of Crystallography texts on crystallography |
| series2 | International Union of Crystallography texts on crystallography |
| spelling | Li, Wai-Kee Verfasser (DE-588)1028491433 aut Advanced structural inorganic chemistry Wai-Kee Li ; Gong-Du Zhou ; Thomas Chung Wai Mak 1. publ. Oxford Oxford Univ. Press 2008 XX, 819 S. Ill., graph. Darst. txt rdacontent n rdamedia nc rdacarrier International Union of Crystallography texts on crystallography 10 Hier auch später erschienene, unveränderte Nachdrucke Chemistry, Inorganic Chemistry, Physical and theoretical Strukturchemie (DE-588)4183790-3 gnd rswk-swf Anorganische Verbindungen (DE-588)4002147-6 gnd rswk-swf (DE-588)4173536-5 Patentschrift gnd-content Strukturchemie (DE-588)4183790-3 s Anorganische Verbindungen (DE-588)4002147-6 s DE-604 Zhou, Gong-Du Verfasser aut Mak, Thomas C. 1936- Verfasser (DE-588)17224661X aut International Union of Crystallography texts on crystallography 10 (DE-604)BV002805877 10 HBZ Datenaustausch application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=016406040&sequence=000002&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA Inhaltsverzeichnis |
| spellingShingle | Li, Wai-Kee Zhou, Gong-Du Mak, Thomas C. 1936- Advanced structural inorganic chemistry International Union of Crystallography texts on crystallography Chemistry, Inorganic Chemistry, Physical and theoretical Strukturchemie (DE-588)4183790-3 gnd Anorganische Verbindungen (DE-588)4002147-6 gnd |
| subject_GND | (DE-588)4183790-3 (DE-588)4002147-6 (DE-588)4173536-5 |
| title | Advanced structural inorganic chemistry |
| title_auth | Advanced structural inorganic chemistry |
| title_exact_search | Advanced structural inorganic chemistry |
| title_exact_search_txtP | Advanced structural inorganic chemistry |
| title_full | Advanced structural inorganic chemistry Wai-Kee Li ; Gong-Du Zhou ; Thomas Chung Wai Mak |
| title_fullStr | Advanced structural inorganic chemistry Wai-Kee Li ; Gong-Du Zhou ; Thomas Chung Wai Mak |
| title_full_unstemmed | Advanced structural inorganic chemistry Wai-Kee Li ; Gong-Du Zhou ; Thomas Chung Wai Mak |
| title_short | Advanced structural inorganic chemistry |
| title_sort | advanced structural inorganic chemistry |
| topic | Chemistry, Inorganic Chemistry, Physical and theoretical Strukturchemie (DE-588)4183790-3 gnd Anorganische Verbindungen (DE-588)4002147-6 gnd |
| topic_facet | Chemistry, Inorganic Chemistry, Physical and theoretical Strukturchemie Anorganische Verbindungen Patentschrift |
| url | http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=016406040&sequence=000002&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA |
| volume_link | (DE-604)BV002805877 |
| work_keys_str_mv | AT liwaikee advancedstructuralinorganicchemistry AT zhougongdu advancedstructuralinorganicchemistry AT makthomasc advancedstructuralinorganicchemistry |