46 A Textbook of Inorganic Chemistry – Volume I

 Trends in Stepwise Constants

The values of stepwise equilibrium constants for the formation of a particular metal-complex
decrease successively in most of the cases i.e. K1 > K2 > K3 > K4 > K5 >....> Kn. This regular decrease in the
values of stepwise formation constants may be attributed to the decrease in the number of coordinated H2O
ligands that are available for the replacement by the attacking ligands. Besides, the continuous decline in the
values of successive stepwise stability constant values may also be attributed to the decreasing ability of metal
ions with a progressive intake of ligands, Coulombic factors and steric hindrance. Consider the following
ligand displacement reaction:

[Cu(H2 O)6 ]2+ + 4NH3 ⇌ [Cu(H2 O)2 (NH3 )4 ]2+ + 4H2 O (20)

[[Cu(H2 O)2 (NH3 )4 ]2+ ][H2 O]4 (21)

𝛽4 =
[[Cu(H2 O)6 ]2+ ][NH3 ]4

The overall process can be supposed to take place through the following steps:

𝐾1 (22)
[Cu(H2 O)6 ]2+ + NH3 ⇌ [Cu(H2 O)5 (NH3 )]2+ + H2 O

[[Cu(H2 O)5 (NH3 )]2+ ][H2 O] (23)

𝐾1 =
[[Cu(H2 O)6 ]2+ ][NH3 ]

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 CHAPTER 2 Metal-Ligand Equilibria in Solution: 47

𝐾2 (24)
[Cu(H2 O)5 (NH3 )]2+ + NH3 ⇌ [Cu(H2 O)4 (NH3 )2 ]2+ + H2 O

[[Cu(H2 O)4 (NH3 )2 ]2+ ][H2 O] (25)

𝐾2 =
[[Cu(H2 O)5 (NH3 )]2+ ][NH3 ]

𝐾3 (26)
[Cu(H2 O)4 (NH3 )2 ]2+ + NH3 ⇌ [Cu(H2 O)3 (NH3 )3 ]2+ + H2 O

[[Cu(H2 O)3 (NH3 )3 ]2+ ][H2 O] (27)

𝐾3 =
[[Cu(H2 O)4 (NH3 )2 ]2+ ][NH3 ]

𝐾4 (28)
[Cu(H2 O)3 (NH3 )3 ]2+ + NH3 ⇌ [Cu(H2 O)2 (NH3 )4 ]2+ + H2 O

[[Cu(H2 O)2 (NH3 )4 ]2+ ][H2 O] (29)

𝐾4 =
[[Cu(H2 O)3 (NH3 )3 ]2+ ][NH3 ]

It has been observed that log K values for K1, K2, K3 and K4 are 4.3, 3.6, 3.0 and 2.3, respectively. This regular
decrease in stepwise stability constants can be attributed to the decreasing site availability for the attack of the
incoming ligand.

Figure 1. Decreasing availability in of coordinated water molecules to get replaced in first to the last step
in octahedral complexes.

In the first step, NH3 can attack all the six-coordination sites while in the last step the number of coordination
sites available for the attack is reduced to three. Hence, stepwise constant, as well as the ease of formation of
the complexes, also decreases as we move from first to the last step of ligand displacement.

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 48 A Textbook of Inorganic Chemistry – Volume I

Now although the decreasing trend in stepwise constants is pretty much common in most of the
complex formation processes, still some exceptions do exist in which it is found that Kn+1 > Kn. This weird
behavior in stepwise equilibrium constants may be explained in terms of some unusual structural deviations
and variations in the electronic structure of the metal center. The deviations in electronic configurations cause
the change in crystal field stabilization energy (CFSE), and therefore, also affect the overall stability of the
metal complex i.e. complex with a large magnitude of CFSE will be more stable and, consequently, will have
higher value of the stepwise formation constants. Consider the following ligand displacement reaction:

[Cd(H2 O)6 ]2+ + 4Br − ⇌ [CdBr4 ]2− + 6H2 O (30)

[[CdBr4 ]2− ][H2 O]6 (31)

𝛽4 =
[[Cd(H2 O)6 ]2+ ][Br − ]4

The overall process can be supposed to take place through the following steps:

𝐾1 (32)
[Cd(H2 O)6 ]2+ + Br − ⇌ [Cd(H2 O)5 Br]1+ + H2 O

𝐾2 (33)
[Cd(H2 O)5 Br]1+ + Br − ⇌ [Cd(H2 O)4 Br2 ] + H2 O

𝐾3 (34)
[Cd(H2 O)4 Br2 ] + Br − ⇌ [Cd(H2 O)3 Br3 ]− + H2 O

𝐾4 (35)
[Cd(H2 O)3 Br3 ]− + Br ⇌ [CdBr4 ]2− + 3H2 O
−

It has been observed that log K values follows the order K1 > K2 > K3 < K4, instead of K1 > K2 > K3 > K4. This
unusually high value of K4 is because the last step is actually pretty much favored by the release of three aquo
ligands and some simultaneous structural and electronic changes.
Similarly, consider the formation of [Fe(bpy)3]2+ complex:

𝐾1 (36)
[Fe(H2 O)6 ]2+ + bpy ⇌ [Fe(H2 O)4 (bpy)]2+ + 2H2 O

𝐾2 (37)
[Fe(H2 O)4 (bpy)]2+ + bpy ⇌ [Fe(H2 O)2 (bpy)2 ]2+ + 2H2 O

𝐾3 (38)
[Fe(H2 O)2 (bpy)2 ]2+ + bpy ⇌ [Fe(bpy)3 ]2+ + 2H2 O

It has been observed that log K values follow the order K1 > K2 < K3, instead of K1 > K2 > K3. This unusually
high value of K3 is because the complexes formed during first two steps are high spin due to weak H2O ligands
with a CFSE of −0.4∆O (t2g4 eg2), while the last complex [Fe(bpy)3]2+ is low spin with a CFSE value of −2.4∆O
(t2g6 eg0). Hence, large crystal field stabilization in the last step makes K3 even greater than K2.

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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 ............................................................................................................................................. 471