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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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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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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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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