Index - A Textbook of Inorganic Chemistry – Volume 1
INDEX
A
C
Acid hydrolysis ................................................... 86
Calculation of magnetic moments ................... 354
Effect of the leaving group ............................. 87
Experimental magnetic moments ................ 354
Solvation energy of the intermediate .............. 87
Theoretical magnetic moments .................... 357
Steric hindrance .............................................. 87
Carboranes ....................................................... 407
Antiferromagnetic coupling.............................. 379
Arachno ....................................................... 409
Antiferromagnetic materials ............................. 351
Closo ............................................................ 407
Application of magnetochemistry .................... 370
Nido ............................................................. 408
Determination of electronic configuration ... 371
Structural correlation between closo, nido and
Determination of oxidation state .................. 370
arachno carboranes .................................. 410
Determination of stereochemistry ................ 371
Charge transfer spectra .................................... 328
Ligand to ligand charge transfer (LLCT) .... 335
B
Ligand to metal charge transfer (LMCT) .... 328
Base hydrolysis................................................... 87
Hydroly of the complex ions without acidic
Metal to ligand charge transfer (MLCT) ..... 333
Metal to metal charge transfer (MMCT) ..... 334
protons ........................................................ 89
Chelate effect or chelation ................................. 56
Hydrolysis of anionic complexes ................... 89
Applications of chelate complexes ................ 63
Nucleophilic strength...................................... 89
Characteristic features of chelates ................. 56
Bent¡¯s Rule ......................................................... 36
Ligand type .................................................... 56
Bond angles .................................................... 37
Stability of chelates........................................ 58
Bond lengths ................................................... 38
Thermodynamic origin of chelation .............. 60
Coupling constants ......................................... 39
Correlation and spin-orbit coupling in free ions
Exceptions ...................................................... 41
for 1st series of transition metals ................. 243
Inductive effect ............................................... 40
d1 and d9 ions ............................................... 243
Berry-pseudorotation .......................................... 81
d2 and d8 ions ............................................... 244
Body centred close packing .............................. 158
d3 and d7 ions ............................................... 245
Bonding in main group compounds.................... 11
d4 and d6 ions ............................................... 246
d5 ions .......................................................... 247
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A Textbook of Inorganic Chemistry ¨C Volume I
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Correlation diagrams ........................................ 248
Spectroscopic methods .................................. 64
d1 and d9 systems .......................................... 251
Diamagnetic materials ..................................... 349
d2 and d8 systems .......................................... 252
d¦Ð¨Cp¦Ð Bonds ...................................................... 23
d3 and d7 systems .......................................... 254
Molecules with d-valence shell ..................... 23
d and d systems .......................................... 256
Molecules with p-valence shell ..................... 26
4
6
d5 systems ..................................................... 258
Cross exchange reactions ................................. 117
E
Crystal structure of some binary compounds ... 154
Effect of distortion on d-orbital energy levels . 300
Antifluorite ................................................... 160
Antirutile....................................................... 162
BiI3 ................................................................ 167
CdI2 ............................................................... 165
Corundum ..................................................... 172
4-coordinated complexes ............................. 304
6-coordinated complexes ............................. 300
Rhombic distortion ...................................... 303
Tetragonal distortion.................................... 301
Trigonal distortion ....................................... 304
Cristobalite ................................................... 163
Electron exchange reactions ............................ 117
Fluorite ......................................................... 159
Electron transfer reactions ............................... 106
Mn2O3 ........................................................... 170
ReO3 ............................................................. 169
Rutile ............................................................ 161
Crystal structure of some ternary compounds .. 154
Calcite ........................................................... 176
Ilmenite ......................................................... 175
Peroveskite ................................................... 173
Cubic close packing .......................................... 157
Curie temperature ..................................... 345, 377
Curie-Weiss law ............................................... 345
Inner sphere electron transfer mechanism ... 112
Outer sphere electron transfer mechanism... 106
Electronic spectra of molecular addition
compounds ................................................... 336
Electronic spectra of transition metal complexes
..................................................................... 214
Electrophilic attack on ligands........................... 92
Elementary theory of magneto-chemistry........ 342
Basic terminology ........................................ 343
Classes of magnetic materials ...................... 349
Classical concept of magnetism................... 344
D
Quantum mechanical concept of magnetism 346
Decarboxylation ................................................. 92
Evidences for the covalent character in metal¨C
Determination of binary formation constants ..... 63
ligand bond .................................................. 180
Job's method ................................................... 65
EPR spectra.................................................. 181
Method of variation ........................................ 65
Lande's splitting factor................................. 181
pH-metric method........................................... 63
Nephelauxetic effect .................................... 180
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INDEX
473
NMR spectra................................................. 181
Ferrimagnetic materials ................................... 381
Nuclear quadrupole resonance...................... 182
Ferromagnetic coupling ................................... 376
Superexchange .............................................. 182
Ferromagnetic materials .................................. 350
Formation constants ........................................... 44
F
Overall formation constants ........................... 44
Factors affecting stability of metal complexes ... 49
Backbonding by ligand ................................... 53
Basicity of the ligand ...................................... 53
Stepwise formation constants ........................ 44
Trends in stepwise constants ......................... 46
Frank-Condon principal ................................... 108
Charge on the ligand ....................................... 52
G
Charge on the metal ion .................................. 50
Chelating effect of ligand ............................... 54
Gouy balance ................................................... 351
Class of the metal ion ..................................... 51
Guoy's method for measuring magnetic
Concentration of ligand .................................. 55
susceptibility ................................................ 351
Dipole moment of ligand ................................ 54
Ionic Potential................................................. 50
H
Macrocyclic effect of ligand ........................... 55
Heteropoly acids and salts ........................123, 144
Nature of the ligand ........................................ 52
Nature of the metal ion ................................... 49
Size of the ligand ............................................ 52
Size of the metal ion ....................................... 49
Special configuration of ligand....................... 54
Steric effect of ligand ..................................... 53
Factors affecting the stability of chelate
complexes ....................................................... 60
Charge on the ligand ....................................... 62
Lewis base strength of the ligand ................... 62
Nature of the metal ion ................................... 61
Number of chelate rings ................................. 61
Resonance effect ............................................. 61
Size of the chelate ring ................................... 60
Steric hindrance of the ligands ....................... 62
Steric strain in the ligand ................................ 62
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1:12 (icosahedral heteroatom) ..................... 150
1:12 (tetrahedral heteroatom) ...................... 145
1:6 (octahedral heteroatom) ......................... 147
1:9 (octahedral heteroatom) ......................... 148
2:18 (tetrahedral heteroatom) ...................... 146
Heteropoly anions
[As2M18O62]6?............................................... 146
[CoW12O40]6? ............................................... 146
[CoW12O50]5? ............................................... 146
[GeM12O40]4? ................................................ 145
[NaP5W36O110]14? ......................................... 151
[NiMo9O32]6?................................................ 148
[P2M18O62]6? ................................................. 146
[SiM12O40]4? ................................................. 145
Hexagonal close packing ................................. 154
High nuclearity carbonyl clusters .................... 418
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A Textbook of Inorganic Chemistry ¨C Volume I
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Electron counting scheme............................. 418
Labile complexes ........................................... 71
Hybridization ...................................................... 28
Outer orbital complexes ................................. 71
BeCl2............................................................... 31
SN1 or dissociative pathway .......................... 72
BF3 .................................................................. 32
SN2 or associative pathway............................ 74
CCl2Me2 .......................................................... 37
Inner sphere electron transfer mechanism ....... 112
CH4 ................................................................. 32
Bridging complex ........................................ 114
dsp2 ................................................................. 34
Electronic configuration .............................. 115
H2O ................................................................. 36
Nature of the bridging ligand ....................... 116
Main features .................................................. 31
Intensity of magnetization ............................... 343
PbF2Me2 .......................................................... 37
Irving-William series ......................................... 49
PF5 .................................................................. 33
Isopoly acids and salts ..................................... 123
SF4 .................................................................. 37
Decamolybdate ............................................ 133
SF6 .................................................................. 33
Dimolybdate ................................................ 127
SiCl2Me2 ......................................................... 37
Heptamolybdate ........................................... 128
SOF4 ............................................................... 37
Hexamolybdate ............................................ 132
sp .....................................................................31
Hexatungstate .............................................. 143
sp ................................................................... 32
Metamolybdate ............................................ 128
sp3d ........................................................... 33, 35
Metatungstate............................................... 140
sp3d2 .......................................................... 33, 35
Mo36-polymolybdate .................................... 135
sp d .......................................................... 34, 35
Octamolybdate ............................................. 129
TiMe2Cl2 ......................................................... 41
Paramolybdate ............................................. 128
Types of hybridization .................................... 31
Paratungstate ................................................ 137
3
3 3
Paratungstate B ............................................ 139
I
Tetramolybdate ............................................ 128
Inert and labile complexes .................................. 70
Evidences for the lability and inertness .......... 72
Factors affecting the kinetic stability or lability
of non-transition metal complexes ............. 75
From crystal field theory ................................ 71
From valence bond theory .............................. 71
Inert complexes .............................................. 72
Inner orbital complexes .................................. 71
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Tetratungstate .............................................. 144
Trimolybdate ............................................... 127
Tungstate Y.................................................. 141
Isopoly anions .................................................. 123
[Cr2O7]2? ...................................................... 123
[Cr3O10]2? ..................................................... 123
[Cr4O13]2? ..................................................... 123
[H2W12O40]6? ................................................ 140
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INDEX
475
[H2W12O42]10?................................................ 137
Charge to ionic-size ratio ............................... 76
[Mo10O34]8? ................................................... 133
Geometry of the complex .............................. 76
[Mo2O7]2? ...................................................... 127
Radii of central metal ion .............................. 75
[Mo3O10]2? .................................................... 127
Ligand cone angle ............................................ 465
[Mo4O13] .................................................... 128
Ligand displacement mechanism in octahedral
2?
[Mo6O19]2? .................................................... 133
complexes ...................................................... 77
[Mo7O24]6? .................................................... 128
Interchange .................................................... 79
[Mo8O26]4? ............................................ 128, 129
SN1 mechanism.............................................. 77
[Mo8O26] .................................................... 133
SN2 mechanism .............................................. 78
8?
[W10O32]4? ..................................................... 141
Ligand displacement mechanism in square planar
[W4O16]8? ...................................................... 144
complexes .................................................80, 96
[W6O19]2? ...................................................... 143
Normal SN2 pathway ..................................... 97
[W7O24] .............................................. 135, 137
Solvent assisted SN2 pathway ........................ 96
6?
Ligand field splitting........................................ 280
J
d1 complexes ................................................ 280
Jahn-Tellar effect .............................................. 312
Consequences of Jahn-Teller distortion ....... 322
Effect on the electronic spectra .................... 318
Energetics of Jahn-Teller distortion ............. 313
Static and dynamic distortion ....................... 321
K
d2 complexes ................................................ 282
d3 complexes ................................................ 288
d4 complexes ................................................ 294
d5 complexes ................................................ 298
d6 complexes ................................................ 296
d7 complexes ................................................ 291
d8 complexes ................................................ 285
Keggin structure ............................................... 145
Kinetic stability .................................................. 70
Non-transition metal complexes ..................... 75
Transition metal complexes ............................ 71
Kramers-Anderson superexchange ................... 182
d9 complexes ................................................ 281
Limitations of crystal field theory ............180, 183
Lipscomb's model involving STYX numbers.. 391
Loadstone..................................................342, 381
Low nuclearity carbonyl clusters ..................... 412
Dinuclear ..................................................... 413
Tetranuclear ................................................. 415
L
Lability or inertness of non-transition metal
Trinuclear..................................................... 414
complexes ....................................................... 75
Charge on the central metal ion ...................... 75
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