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A TEXTBOOK OF INORGANIC
CHEMISTRY
Volume I

Mandeep Dalal
Publisher:
Dalal Institute, Main Market, Sector-14, Rohtak, Haryana – 124001
www.dalalinstitute.com, +91-9802825820, dr.mandeep.dalal@gmail.com

Distributor:
University Book Centre, Medical Mor, Rohtak, Haryana – 124001
ubc.rohtak@gmail.com, +91-9896144124, +91-9996069983

No part of this book may be reproduced in any written, electronic, recording, or photocopying without written
permission of the publisher or author. The exception would be in the case of brief quotations embodied in the
critical articles or reviews and pages where permission is specifically granted by the publisher or author.

A Textbook of Inorganic Chemistry – Volume I / Mandeep Dalal

Copyright © 2018 by Mandeep Dalal. All Rights Reserved
First published: 2017
Printed in India
ISBN: 978-81-938720-0-0

Although every precaution has been taken to verify the accuracy of the information contained herein, the author
and publisher assume no responsibility for any errors or omissions. No liability is assumed for damages that
may result from the use of information contained within.

Printer:
Acharya Printing Press, Gohana-Rohtak Road, Tej Colony, Rohtak, Haryana – 124001
Dedicated to my mother “Darshana Devi”
This Page is Intentionally Left Blank
 PREFACE
The preface writing has always been a wonderful feeling which cannot be expressed in words as it
relates you to your audience through your work. I conceived the idea of writing a new advanced-level textbook
in inorganic chemistry four years ago when I saw post-graduate chemistry students being tired of their ill-
resourced university or college library in search of the syllabus topics. I had also decided to write the textbooks
of physical and organic chemistry because I think that someone who wants to teach or text one stream must
have the core conceptual understanding of all the three streams of chemical science otherwise one would not
be able to connect and explain the interdisciplinary topics in a comprehensive manner.
Out of the series of three textbooks; the present book, entitled “A Textbook of Inorganic Chemistry
– Volume 1”; is the first instalment of “A Textbook of Inorganic Chemistry” which is a four-volume set in all.
All the students and teachers are advised to read and consult all the four volumes in a subsequent pattern for a
more efficient and productive understanding of the subject of inorganic chemistry.
I also celebrate this opportunity for expressing the bottom hearted gratitude towards the people who
supported me at all stages of my work. First of all, I would like to express my sincere gratitude to my doctoral
supervisors, Prof. S. P. Khatkar and Prof. V.B. Taxak for their continuous support and guidance from day one.
Then I would like to record appreciation to my lovely sister, Jyoti Dalal, for her unconditional love, support
and for being the guiding light when life threw me in the darkest of corners. I am very much thankful to my
beautiful wife, Anita Sangwan, who always stands shoulder to shoulder with me in my good and bad times. I
especially want to thank my brother Sandeep Dalal for his positive criticism, encouragement, motivation and
truly selfless support. A special thanks to my dearest sister Garima Sheoran for her love, care, and all-time
encouragement. I also wish to thank my entire family, friends and teachers for providing a loving environment
for me.
Lastly, and most importantly, I wish to thank my mother, Darshana Devi, who bore me, raised me,
supported me, taught me, and loved me.
Mandeep Dalal
This Page is Intentionally Left Blank
Table of Contents
CHAPTER 1 ................................................................................................................................................. 11
Stereochemistry and Bonding in Main Group Compounds: ................................................................. 11
 VSEPR Theory ............................................................................................................................... 11

 dπ–pπ Bonds ................................................................................................................................... 23

 Bent Rule and Energetic of Hybridization ...................................................................................... 28

 Problems ......................................................................................................................................... 42

 Bibliography ................................................................................................................................... 43

CHAPTER 2 ................................................................................................................................................. 44
Metal-Ligand Equilibria in solution: ...................................................................................................... 44
 Stepwise and Overall Formation Constants and Their Interactions ................................................ 44

 Trends in Stepwise Constants ......................................................................................................... 46

 Factors Affecting Stability of Metal Complexes with Reference to the Nature of Metal Ion and
Ligand .................................................................................................................................................... 49

 Chelate Effect and Its Thermodynamic Origin ............................................................................... 56

 Determination of Binary Formation Constants by pH-metry and Spectrophotometry .................... 63

 Problems ......................................................................................................................................... 68

 Bibliography ................................................................................................................................... 69

CHAPTER 3 ................................................................................................................................................. 70
Reaction Mechanism of Transition Metal Complexes-I: ....................................................................... 70
 Inert and Labile Complexes ............................................................................................................ 70

 Mechanisms for Ligand Replacement Reactions ............................................................................ 77

 Formation of Complexes from Aquo Ions ...................................................................................... 82
 Ligand Displacement Reactions in Octahedral Complexes- Acid Hydrolysis, Base Hydrolysis..... 86

 Racemization of Tris Chelate Complexes ....................................................................................... 89

 Electrophilic Attack on Ligands ..................................................................................................... 92

 Problems ......................................................................................................................................... 94

 Bibliography ................................................................................................................................... 95
CHAPTER 4 ................................................................................................................................................. 96
Reaction Mechanism of Transition Metal Complexes-II: ..................................................................... 96
 Mechanism of ligand displacement reactions in square planar complexes ..................................... 96

 The Trans Effect ............................................................................................................................. 98

 Theories of Trans Effect ............................................................................................................... 103

 Mechanism of Electron Transfer Reactions – Types; Outer Sphere Electron Transfer Mechanism and
Inner Sphere Electron Transfer Mechanism ......................................................................................... 106
 Electron Exchange ........................................................................................................................ 117

 Problems ....................................................................................................................................... 121

 Bibliography ................................................................................................................................. 122

CHAPTER 5 ............................................................................................................................................... 123

Isopoly and Heteropoly Acids and Salts: .............................................................................................. 123
 Isopoly and Heteropoly Acids and Salts of Mo and W: Structures of Isopoly and Heteropoly Anions
123

 Problems ....................................................................................................................................... 152

 Bibliography ................................................................................................................................. 153

CHAPTER 6 ............................................................................................................................................... 154

Crystal Structures: ................................................................................................................................. 154
 Structures of Some Binary and Ternary Compounds Such as Fluorite, Antifluorite, Rutile, Antirutile,
Crystobalite, Layer Lattices - CdI2, BiI3; ReO3, Mn2O3, Corundum, Pervoskite, Ilmenite and Calcite. 154
 Problems ....................................................................................................................................... 178

 Bibliography ................................................................................................................................. 179

CHAPTER 7 ............................................................................................................................................... 180

Metal-Ligand Bonding: .......................................................................................................................... 180
 Limitation of Crystal Field Theory ............................................................................................... 180

 Molecular Orbital Theory – Octahedral, Tetrahedral or Square Planar Complexes ...................... 184

 π-Bonding and Molecular Orbital Theory..................................................................................... 198

 Problems ....................................................................................................................................... 212

 Bibliography ................................................................................................................................. 213

CHAPTER 8 ............................................................................................................................................... 214
Electronic Spectra of Transition Metal Complexes: ............................................................................ 214
 Spectroscopic Ground States ........................................................................................................ 214

 Correlation and Spin-Orbit Coupling in Free Ions for 1st Series of Transition Metals ................. 243

 Orgel and Tanabe-Sugano Diagrams for Transition Metal Complexes (d1 – d9 States) ................ 248

 Calculation of Dq, B and β Parameters ......................................................................................... 280

 Effect of Distortion on the d-Orbital Energy Levels ..................................................................... 300

 Structural Evidence from Electronic Spectrum ............................................................................. 307

 Jahn-Tellar Effect ......................................................................................................................... 312

 Spectrochemical and Nephelauxetic Series................................................................................... 324

 Charge Transfer Spectra ............................................................................................................... 328

 Electronic Spectra of Molecular Addition Compounds ................................................................ 336

 Problems ....................................................................................................................................... 340

 Bibliography ................................................................................................................................. 341

CHAPTER 9 ............................................................................................................................................... 342

Magnetic Properties of Transition Metal Complexes: ......................................................................... 342
 Elementary Theory of Magneto-Chemistry .................................................................................. 342

 Guoy’s Method for Determination of Magnetic Susceptibility ..................................................... 351

 Calculation of Magnetic Moments ................................................................................................ 354

 Magnetic Properties of Free Ions .................................................................................................. 359

 Orbital Contribution: Effect of Ligand-Field ................................................................................ 362

 Application of Magneto-Chemistry in Structure Determination ................................................... 370

 Magnetic Exchange Coupling and Spin State Cross Over ............................................................ 375
 Problems ....................................................................................................................................... 384

 Bibliography ................................................................................................................................. 385

CHAPTER 10 ............................................................................................................................................. 386

Metal Clusters: ....................................................................................................................................... 386
 Structure and Bonding in Higher Boranes .................................................................................... 386
  Wade’s Rules ................................................................................................................................ 401

 Carboranes .................................................................................................................................... 407

 Metal Carbonyl Clusters- Low Nuclearity Carbonyl Clusters ...................................................... 412

 Total Electron Count (TEC) ......................................................................................................... 417

 Problems ....................................................................................................................................... 424

 Bibliography ................................................................................................................................. 425

CHAPTER 11 ............................................................................................................................................. 426

Metal-Π Complexes:............................................................................................................................... 426
 Metal Carbonyls: Structure and Bonding ...................................................................................... 426

 Vibrational Spectra of Metal Carbonyls for Bonding and Structure Elucidation .......................... 439

 Important Reactions of Metal Carbonyls ...................................................................................... 446

 Preparation, Bonding, Structure and Important Reactions of Transition Metal Nitrosyl, Dinitrogen
and Dioxygen Complexes..................................................................................................................... 450

 Tertiary Phosphine as Ligand ....................................................................................................... 463

 Problems ....................................................................................................................................... 469

 Bibliography ................................................................................................................................. 470

Index

Arachno, 409
A
Closo, 407

Acid hydrolysis, 86 Nido, 408

Application of magnetochemistry, 370 Structural correlation between closo, nido and

Determination of electronic configuration, 371 arachno carboranes, 410

Determination of oxidation state, 370 Charge transfer spectra, 328

Determination of stereochemistry, 371 Ligand to ligand charge transfer (LLCT), 335

Ligand to metal charge transfer (LMCT), 328

B
Metal to ligand charge transfer (MLCT), 333

Base hydrolysis, 87 Metal to metal charge transfer (MMCT), 334

Bent’s Rule, 36 Chelate effect or chelation, 56

Bond angles, 37 Applications of chelate complexes, 63

Bond lengths, 38 Characteristic features of chelates, 56

Coupling constants, 39 Ligand type, 56

Exceptions, 41 Stability of chelates, 58

Inductive effect, 40 Thermodynamic origin of chelation, 60

Correlation and spin-orbit coupling in free ions

C
for 1st series of transition metals, 243

Calculation of magnetic moments, 354 d1 and d9 ions, 243

Experimental magnetic moments, 354 d2 and d8 ions, 244

Theoretical magnetic moments, 357 d3 and d7 ions, 245

Carboranes, 407 d4 and d6 ions, 246

 d5 ions, 247
D
Correlation diagrams, 248
Determination of binary formation constants, 63
d1 and d9 systems, 251
Job's method, 65
d2 and d8 systems, 252
Method of variation, 65
d3 and d7 systems, 254
pH-metric method, 63
d4 and d6 systems, 256
Spectroscopic methods, 64
d5 systems, 258
dπ–pπ Bonds, 23
Cross exchange reactions, 117
Molecules with d-valence shell, 23
Crystal structure of some binary compounds, 154
Molecules with p-valence shell, 26
Antifluorite, 160

Antirutile, 162
E
BiI3, 167
Effect of distortion on d-orbital energy levels, 300
CdI2, 165
4-coordinated complexes, 304
Corundum, 172
6-coordinated complexes, 300
Cristobalite, 163
Rhombic distortion, 303
Fluorite, 159
Tetragonal distortion, 301
Mn2O3, 170
Trigonal distortion, 304
ReO3, 169
Electron exchange reactions, 117
Rutile, 161
Electron transfer reactions, 106
Crystal structure of some ternary compounds, 154
Inner sphere electron transfer mechanism, 112
Calcite, 176
Outer sphere electron transfer mechanism, 106
Ilmenite, 175
Electronic spectra of molecular addition
Peroveskite, 173
compounds, 336
Electronic spectra of transition metal complexes, Chelating effect of ligand, 54

214 Class of the metal ion, 51

Electrophilic attack on ligands, 92 Concentration of ligand, 55

Elementary theory of magneto-chemistry, 342 Dipole moment of ligand, 54

Basic terminology, 343 Ionic Potential, 50

Classes of magnetic materials, 349 Macrocyclic effect of ligand, 55

Classical concept of magnetism, 344 Size of the ligand, 52

Quantum mechanical concept of magnetism, Size of the metal ion, 49

346 Special configuration of ligand, 54

Evidences for the covalent character in metal– Steric effect of ligand, 53

ligand bond, 180 Factors affecting the stability of chelate

EPR spectra, 181 complexes, 60

Lande's splitting factor, 181 Charge on the ligand, 62

Nephelauxetic effect, 180 Lewis base strength of the ligand, 62

NMR spectra, 181 Nature of the metal ion, 61

Nuclear quadrupole resonance, 182 Number of chelate rings, 61

Superexchange, 182 Resonance effect, 61

Size of the chelate ring, 60

F
Steric hindrance of the ligands, 62

Factors affecting stability of metal complexes, 49 Steric strain in the ligand, 62

Backbonding by ligand, 53 Formation constants, 44

Basicity of the ligand, 53 Overall formation constants, 44

Charge on the ligand, 52 Stepwise formation constants, 44

Charge on the metal ion, 50 Trends in stepwise constants, 46

 G I

Guoy's method for measuring magnetic Inert and labile complexes, 70

susceptibility, 351 Evidences for the lability and inertness, 72

Factors affecting, 75
H
From crystal field theory, 71

Heteropoly acids and salts, 144 From valence bond theory, 71

1:12 (icosahedral heteroatom), 150 Isopoly acids and salts, 123

1:12 (tetrahedral heteroatom), 145 Decamolybdate, 133

1:6 (octahedral heteroatom), 147 Dimolybdate, 127

1:9 (octahedral heteroatom), 148 Heptamolybdate, 128

2:18 (tetrahedral heteroatom), 146 Hexamolybdate, 132

High nuclearity carbonyl clusters, 418 Hexatungstate, 143

Electron counting scheme, 418 Metamolybdate, 128

Hybridization, 28 Metatungstate, 140

dsp2, 34 Mo36-polymolybdate, 135

Main features, 31 Octamolybdate, 129

sp, 31 Paramolybdate, 128

sp3, 32 Paratungstate, 137

sp3d, 33, 35 Paratungstate B, 139

sp3d2, 33, 35 Tetramolybdate, 128

sp3d3, 34, 35 Tetratungstate, 144

Types of hybridization, 31 Trimolybdate, 127

Tungstate Y, 141
 d6 complexes, 296
J
d7 complexes, 291
Jahn-Tellar effect, 312
d8 complexes, 285
Consequences of Jahn-Teller distortion, 322
d9 complexes, 281
Effect on the electronic spectra, 318
Limitations of crystal field theory, 180, 183
Energetics of Jahn-Teller distortion, 313
Lipscomb's model involving STYX numbers, 391
Static and dynamic distortion, 321
Low nuclearity carbonyl clusters, 412

Dinuclear, 413
L
Tetranuclear, 415
Ligand cone angle, 465
Trinuclear, 414
Ligand displacement mechanism in octahedral

complexes, 77 M

Interchange, 79
Magnetic exchange coupling, 375
SN1 mechanism, 77
Magnetic properties of free ions, 359
SN2 mechanism, 78
Magnetic properties of transition metal
Ligand displacement mechanism in square planar
complexes, 342
complexes, 80, 96
Marcus theory of electron transfer, 119
Normal SN2 pathway, 97
Metal aquo complexes, 82
Solvent assisted SN2 pathway, 96
Eight coordinated, 83
Ligand field splitting, 280
Four coordinated, 83
1
d complexes, 280
Important reactions, 84
2
d complexes, 282
Metal-metal bonding, 84
d3 complexes, 288
Nine coordinated, 83
4
d complexes, 294
Six-coordinated, 82
5
d complexes, 298
Metal carbonyl clusters, 412, 428 Preparation, 455

[Re4(CO)16]2−, 429 Reactions, 459

Co2(CO)8, 428 Structure, 458

Co6(CO)16, 429 Metal dioxygen complexes, 459

Fe2(CO)9, 428 Bonding, 460

Fe3(CO)12, 429 Preparation, 459

High nuclearity (HNCC), 412 Reactions, 463

Ir4(CO)12, 429 Structure, 462

Low nuclearity (LNCC), 412 Metal nitrosyl complexes, 450

M4(CO)12, 429 Bonding, 451

M2(CO)10, 428 Prepartion, 450

M3(CO)12, 429 Reactions, 455

Os4(CO)14, 429 Structure, 454

Os4(CO)15, 429 Metal-π complexes, 426

Os4(CO)16, 429 Molecular orbital theory, 184

Rh6(CO)16, 429 Octahedral complexes (pi-bonding), 199

Metal carbonyls, 426 Octahedral complexes (sigma-bonding), 185

Bonding, 431 Square planar complexes (pi-bonding), 209

Important reactions, 446 Square planar complexes (sigma-bonding), 195

Methods of preparation, 426 Tetrahedral complexes (pi-bonding), 206

Structure, 428 Tetrahedral complexes (sigma bonding), 192

Metal clusters, 386

N
Metal dinitrogen complexes, 455

Bonding, 456 Nephelauxetic ratio, 280

 d1 complexes, 280 d5 systems, 269

d2 complexes, 282
R
d3 complexes, 288

d4 complexes, 294 Racah parameter, 280

d5 complexes, 298 d1 complexes, 280

d6 complexes, 296 d2 complexes, 282

d7 complexes, 291 d3 complexes, 288

d8 complexes, 285 d4 complexes, 294

d9 complexes, 281 d5 complexes, 298

Nephelauxetic series, 326 d6 complexes, 296

Nephelauxetic order of ligands, 328 d7 complexes, 291

Nephelauxetic order of metals, 328 d8 complexes, 285

d9 complexes, 281
O
Racemization of tris chelate complexes, 89

Orbital contribution to magnetic moment, 362 Bailer twist, 90

Effect of spin orbital coupling, 367 Ray-Dutt twist, 90

Ligand field effect in octahedral complexes, Reactions of metal carbonyls, 446

363 Disproportionation reaction, 449

Ligand field effect in tetrahedral complexes, Formation of carbonylate anions, 447

365 Formation of carbonylate cations, 448

Temperature independent paramagnetism, 369 Formation of metal carbonyl nitrosyls or metal

Orgel diagrams, 248, 259 nitrosyls, 449

d1, d9, d4, d6 systems, 259 Ligand displacement, 446

d2, d8, d3, d7 systems, 264

 Synthesis of metal carbonyl halides or metal Hexaborane-10 (B6H10), 397

halides, 448 Molecular orbital treatment of 3-centre-2-

synthesis of metal carbonyl hydrides, 448 electron bond, 387

Pentaborane-11 (B5H11), 396

S
Pentaborane-9 (B5H9), 395

Self exchange reactions, 117 Structural correlation between closo, nido and

Spectrochemical series, 324 arachno boranes, 399

Spectrochemical order of ligands, 325 Tetraborane-10 (B4H10), 394

Spectrochemical order of metals, 325 Valence bond treatment of 3-centre-2-electron

Spectroscopic ground states, 214 bond, 386

Atomic term symbols, 219

T
Calculation of microstates, 214

Derivation of term symbols when electrons are Tanabe-Sugano diagrams, 248, 271

present in same subshell, 225 d1 configuration, 272

Determination of spectroscopic ground state d2 configuration, 273

term, 240 d3 configuration, 274

Spin state crossover, 382 d4 configuration, 275

Structural evidence from electronic spectrum, 307 d5 configuration, 276

Molar absorptivity of assigned bands, 307 d6 configuration, 277

Splitting pattern of assigned bands, 309 d7 configuration, 278

Structure and bonding in higher boranes, 386 d8 configuration, 279

Classification of bonds present in higher d9 configuration, 272

boranes, 390 Tertiary phosphine as ligand, 463

Decaborane-14 (B10H14), 398 Bonding, 464

 Electronic properties, 465 Structural prototype, 440

Preparation, 463 Study of reaction kinetics, 446

Reactivity, 463 Tolman electronic parameter, 440

Steric properties, 465 VSEPR Theory, 11

Structure, 464 Application to molecular geometries, 14

Tolman electronic parameter, 466 AXE method, 21

Total electron count (TEC), 417 Basic postulates, 13

Correlation between TEC and SEP, 423 BeCl2 molecule, 14

Isolobal analogy, 418 BF3 molecule, 14

Trans effect, 98 BrF5 molecule, 19

Applications of trans effect, 99 CH4 molecule, 15

Kinetic trans effect, 98 ClF3 molecule, 17

Pi-bonding theory, 104 H2O molecule, 16

Polarization theory, 103 I3− molecular ion, 18

Theories of trans effect, 103 IF7 molecule, 20

Thermodynamic trans effect, 99 Lewis concept of electron pair sharing, 11

Trans effect series, 98 Limitations of VSEPR model, 23

Mendeleev’s periodic table, 11

V
NH3 molecule, 15

Vibrational spectra of metal carbonyls, 439 PF5 molecule, 16

Calculation of CO bond order, 445 Points on the sphere model, 12

Differentiation of bridging and terminal SF4 molecule, 16

carbonyls, 444 SF6 molecule, 18

Pi-basicity of metal centre, 439 SO2 molecule, 14

Tangent sphere model, 12
W
XeF4 molecule, 19
Wade's rules, 401
XeF5− molecular ion, 21
4n rule, 401
XeOF5− molecular ion, 20
5n rule, 405

6n rule, 406
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