Q.

Molecular addition compounds, double salts and coordination compounds

coordination sphere,coordination number (C.N), oxidation state (O.S.) of the
central metal atom.
1.Molecular addition compounds are compounds formed by the physical combination
of two or more simpler molecules in a definite ratio. They are not held together by
covalent bonds, but by weaker intermolecular forces, such as London dispersion forces,
dipole-dipole interactions, or hydrogen bonding.
There are two main types of molecular addition compounds:

Clathrates: These are inclusion compounds in which one molecule (the host) forms a
cage-like structure that traps another molecule (the guest) inside. Clathrates are often
formed between water molecules and organic molecules, such as cyclodextrins.

Hydrates: These are compounds that contain water molecules as part of their crystal
structure. Hydrates are very common, and many inorganic salts form hydrates when
they are crystallized from water. For example, copper sulfate pentahydrate
(CuSO₄·5H₂O) is a hydrate that contains five water molecules for every molecule of
copper sulfate.

Molecular addition compounds have a variety of properties that are different from the
properties of the individual molecules that make them up. For example, hydrates often
have lower melting points than the anhydrous salts from which they are formed. This is
because the hydrogen bonds between the water molecules and the ions in the salt
disrupt the ionic lattice, making it easier for the ions to move and melt.

Molecular addition compounds have a wide variety of applications.

They are used in the food industry, the pharmaceutical industry, and the chemical
industry. For example, clathrates are used to encapsulate flavors and fragrances in food
products. Hydrates are used as desiccants, dryingn agents, and refrigerants.
2.Double Salt and coordination compounds :-

Both double salts and coordination compounds are types of chemical compounds, but
they have distinct differences in their structure, properties, and behavior.
Double salts:
Are a mixture of two or more distinct salts that crystallize together in the same crystal
lattice. Dissociate completely into their individual ions when dissolved in water.
Have properties that are essentially the sum of the properties of their
constituent salts. Do not exhibit unique colors or magnetic properties. An example of a
double salt is potash alum, KAl(SO₄)₂•12H₂O.

Coordination compounds:

Are also known as coordination complexes and are formed by the coordination of a
central metal ion or atom with surrounding ligands. Ligands are molecules or ions that
donate electron pairs to the metal ion, forming coordinate covalent bonds.
Exist as distinct entities in both solid and dissolved states. Often have unique colors,
magnetic properties, and reactivities that are not present in the free metal ions or
ligands. An example of a coordination compound is copper(II) sulfate pentahydrate,
CuSO₄•5H₂O. Image of Copper(II) sulfate pentahydrate, CuSO₄•5H₂o . Here's a table
summarizing the key differences between double salts and coordination compounds:

3.Coordination sphere and coordination number (cn).

● The coordination sphere consists of the central metal ion or atom plus its
attached ligands, which are molecules or ions that donate electrons to the metal.

● The coordination number is the number of donor atoms (not ligands) bonded to
the metal. For example, in the complex [Co(NH3)6]3+, the coordination sphere
is [Co(NH3)6] and the coordination number is 6, because there are six nitrogen
atoms (from NH3) bonded to the cobalt ion.

The coordination sphere and the coordination number depend on severalb factors, such
as the size and charge of the metal , the size and charge of the ligands, the steric
effects, and the stability of the metal-ligand bonds.
Different metals tend to exhibit preferred coordination numbers, which can range from 2
to 1212 The shape and geometry of the coordination sphere also vary according to the
coordination number and the type of ligands. Some common geometries are linear,
trigonal planar, tetrahedral, square planar, octahedral, trigonal bipyramidal, and square
pyramidal.

4.Oxidation State (O.S.) of the Central Metal Atom.

In coordination compounds, the central metal atom exhibits specific oxidation states to
balance the charges of the surrounding ligands. Here's a general approach to determine
the O.S.:
● Assign formal charges to each atom based on their group electronegativity.
 ● More electronegative atoms typically carry negative charges, while less
electronegative atoms may have positive charges.
● Treat the complex ion as a neutral entity.
Sum the charges of all ligands and add it to the complex ion's charge (which is usually 0
for neutral complexes). Set the sum equal to the oxidation state of the central metal
atom and solve for x.
Example:
[Cu(NH3)4]SO4
Cu: +2; NH3: 0; SO4: -2 (formal charges)
Overall charge: 0
4(0) + (-2) = x
x = +2 (oxidation state of Cu)

Q. ligands and classification of ligands, chelating ligands, chelates and their

stability.

Ligands are molecules or ions that play a vital role in coordination chemistry by donating lone
pairs of electrons to a central metal atom or ion. These interactions lead to the formation of
coordination complexes, which are essential in various biological processes like oxygen
transport in hemoglobin and electron transfer in chlorophyll during photosynthesis.

One key classification system for ligands revolves around their capacity to donate electron
pairs, known as denticity. Here's a breakdown of the different types:

● Monodentate ligands: These ligands can donate just one lone pair of electrons to the metal
ion. Examples include chloride (Cl-), water (H2O), and ammonia (NH3). Imagine a
single-headed attachment between the ligand and the metal.
● Bidentate ligands: As the name suggests, these ligands can form two coordination sites
with the central metal ion by donating two lone pairs. Ethylenediamine (en) and oxalate
(C2O42-) are examples of bidentate ligands, which can be pictured as having two "arms" that
clasp the metal ion.
● Tridentate ligands: These ligands take things a step further by donating three lone pairs of
electrons. Bipyridine (bipy) is a classic example of a tridentate ligand, resembling a
three-pronged claw that chelates the metal ion.
● Polydentate ligands: These versatile ligands are capable of donating four or more lone
pairs of electrons. A prominent example is EDTA (ethylenediaminetetraacetic acid), which
boasts six potential donor atoms. Polydentate ligands can be visualized as having multiple
arms or tentacles that wrap around the metal ion.

Chelating ligands are a fascinating subgroup within the polydentate family. They possess a
unique ability to wrap around a metal ion and form a ring-like structure, enclosing the metal
center. The resulting complex is called a chelate. Chelation is a significant process in both
chemistry and biology, as it significantly enhances the stability of the complex.

This stability boost is attributed to the chelate effect. It refers to the increased stability observed
in a complex due to the formation of multiple bonds between the chelating ligand and the central
metal ion. Several factors contribute to the chelate effect:

● Entropy changes: Complex formation involving a chelating ligand leads to a decrease in

entropy (randomness) in the system. This decrease, however, is often outweighed by the
favorable energetic interactions between the ligand and metal ion, resulting in a more stable
complex.
● Lattice energy: When a chelate complex forms, the ions involved are arranged in a crystal
lattice. Chelation often reduces the overall lattice energy of the complex, making it more
thermodynamically favorable and thus, more stable.

Here's a deeper dive into some of the key factors affecting chelate stability:

● Number of donor atoms: The more donor atoms a ligand possesses, the more bonds it can
form with the metal ion, leading to a more stable chelate.
● Metal ion size and charge: Larger metal ions can better accommodate chelating ligands,
allowing for stronger interactions and increased stability. Additionally, ions with higher
charges tend to form stronger bonds with ligands, again contributing to chelate stability.
● Chelate ring size and geometry: Five- and six-membered chelate rings are generally the
most stable. This is because these ring sizes experience minimal strain compared to smaller
or larger rings, allowing for optimal bonding interactions.

Q. Werner's Theory of Coordination Compounds

Alfred Werner, a Swiss chemist, revolutionized our understanding of complex molecules with his
theory of coordination compounds, proposed in 1893. This theory provided a framework for
what we know today about these fascinating structures.

Here are the key postulates of Werner's theory:

● Central Metal Atom: At the heart of a coordination compound lies a central metal atom or
ion.
● Ligands and Bonding: Surrounding this central metal atom or ion are atoms or ions called
ligands. These ligands form coordinate covalent bonds with the metal atom, donating both
electrons involved in the bond. This creates the central entity, known as the coordination
sphere.

● Primary and Secondary Valency: Werner proposed two types of valances for the metal
atom.
● Primary valency (also called ionizable valency) is responsible for forming ionic bonds with
anions outside the coordination sphere.
● Secondary valency (also called non-ionizable valency or coordination number) is
responsible for bonding with ligands within the coordination sphere. The coordination number
represents a fixed number of ligand attachment points for a specific metal ion.
● Isomerism: A significant contribution of Werner's theory was explaining the existence of
isomers. Coordination compounds can exhibit isomerism, meaning they can have the same
chemical formula but different arrangements of atoms or ligands in space. This can lead to
distinct properties despite having the same overall composition.
Werner's theory successfully explained the existence of isomers and the stability of coordination
compounds. It provided a much-needed framework for understanding these complex structures.

Limitations of Werner's Theory

While Werner's theory was a major breakthrough, it had some limitations that later theories
addressed:

● Bonding Nature: A key limitation was the inability to explain the exact nature of the bonding
between the metal atom and the ligands. Werner's theory laid out the concept of coordinate
covalent bonds, but a more detailed understanding of electron configurations and orbital
interactions was needed.
● Not Universally Applicable: The theory couldn't explain why not all elements form
coordination compounds. Some elements lack the appropriate electronic configurations to
effectively form stable coordination spheres with ligands.
● Geometry Limitations: The theory struggled to explain the specific geometries observed in
coordination compounds, particularly those with a coordination number of 4. Werner's theory
primarily focused on simpler geometries, and later theories provided a more comprehensive
explanation for the diverse geometries observed.
● Magnetic and Optical Properties: The theory couldn't explain the magnetic and optical
properties of coordination compounds. These properties are directly related to the electronic
configuration of the metal ion and its interactions with the ligands, which Werner's theory
didn't fully address.

The development of Valence Bond Theory and Crystal Field Theory later addressed these
limitations. These theories provided a more comprehensive understanding of the electronic
structures, bonding nature, and properties of coordination compounds.

Q.Effective atomic number (EAN) rule nomenclature of coordination compounds,

isomerism in coordination compounds.

Effective Atomic Number (EAN) Rule :

The EAN rule, also known as the 18-electron rule, is a powerful concept in coordination
chemistry that sheds light on the stability of these fascinating molecules. It revolves around the
central metal atom and its quest to achieve a stable electron configuration similar to its nearest
noble gas counterpart.

EAN in detail:

● Effective Atomic Number (EAN): This theoretical value represents the total number of
electrons surrounding the central metal atom in a complex. It's a combined effect of the
metal's own valence electrons and the electrons donated by the ligands when they form
coordination bonds with the metal.
● Formula: EAN = Z - X + 2Y
 ○ Z = Atomic number of the metal atom (number of protons)
○ X = Oxidation state of the metal ion (representing the electrons lost)
○ Y = Coordination number (number of ligands bonded to the metal)

Predicting Stability: The EAN rule suggests that coordination compounds achieve greater
stability when the EAN around the central metal atom reaches a value close to the nearest
noble gas in the same period of the periodic table. Common benchmarks for stability are:

● 18 (for transition metals in the 3rd period) - This corresponds to a full valence shell, akin to
noble gases like Argon (Ar).
● 36 (for transition metals in the 4th period) - This is equivalent to having electrons filled in both
the valence shell and the d-subshell, resembling Krypton (Kr).
● 54 (for transition metals in the 5th period) - This value reflects the filling of valence, d, and f
orbitals, mirroring the configuration of Xenon (Xe).

Beyond Prediction: The EAN rule offers more than just predicting the number of ligands a
metal might bind with. It can also help us:

● Rationalize existing structures: By calculating the EAN of a known coordination

compound, we can understand why the observed number of ligands provides stability.
● Predict the relative stability of isomers: If a metal ion can form multiple coordination
isomers with different ligand arrangements, the EAN rule can help predict which isomer is
likely to be more stable based on achieving a closer EAN to a noble gas.

Limitations: While the EAN rule is a valuable tool, it's important to remember that it's a guiding
principle, not an absolute rule. There can be exceptions due to factors like:

● Steric effects: The bulky size of certain ligands can influence the number of ligands a metal
can accommodate, even if it doesn't fulfill the ideal EAN.
● Kinetic factors: Sometimes, the formation of a complex might be kinetically favored even if it
doesn't strictly follow the EAN rule. However, the complex might eventually convert to a more
stable form that adheres to the EAN principle.

Nomenclature of Coordination Compounds - A

systematic approach
Naming coordination compounds follows a set of well-defined rules established by IUPAC to
ensure clear and unambiguous communication. Here's a breakdown of the steps involved:

1. Cation Identification: If the complex ion has a positive charge (cation), start by naming it
first.
2. Metal Designation: Then, move on to the central metal atom and use its elemental name
as you would in a simple ionic compound.
3. Oxidation State: If the metal ion has multiple oxidation states, specify its charge in Roman
numerals enclosed in parentheses following the metal name. This helps differentiate
between complexes with the same metal but different oxidation states.
 4. Ligand Nomenclature: Now it's time for the surrounding ligands. Specific prefixes indicate
the number of each ligand attached (e.g., di-, tri-, tetra-). For anionic ligands (negatively
charged), the name typically ends with the suffix "-ate" or "-ide". Neutral ligands use their
normal names.
5. Overall Charge: If the entire complex ion carries a charge, indicate it after the complete
name of the complex ion using an Arabic numeral enclosed in parentheses.

For instance:

● [Fe(CN)₆]³⁻: This translates to Hexacyanoferrate(III) ion. Here, "hexa" signifies six cyanide
(CN⁻) ligands surrounding the central iron (Fe) atom. The Roman numeral (III) specifies the
+3 oxidation state of iron, and the overall negative charge of the complex is denoted by "-3".
● [Co(NH₃)₄Cl₂]⁺: This translates to Tetraamminedichlorocobalt(II) ion. The complex has four
ammonia (NH₃) and two chloride (Cl⁻) ligands bonded to the cobalt (Co) center. The (II)
indicates a +2 charge on cobalt, and the complex itself carries a +1 charge.

Remember, the EAN rule is a powerful tool for understanding and predicting the behavior

Valances bond theory

Valence Bond Theory (VBT)

This theory is mainly due to Pauling. It deals with the electronic structure of the central
metal ion in its ground state, kind of bonding, geometry and magnetic properties of the
complexes.

Valence bond theory provides an explanation for the structure and magnetic
characteristics of a large number of coordination compounds. The valence bond theory
was used to explain the structure of coordination molecules and their bond connections.

When a metal atom or ion is impacted by ligands, it can utilize its (n–1)d, ns, np, nd
orbitals for hybridization, resulting in a set of equivalent orbitals of definite geometry
such as octahedral, tetrahedral, square planar, and so on. The orbitals of the ligands
that can provide electron pairs for bonding may overlap with the hybridised orbitals.

Assumptions of valence bond theory :

1. The central metal atom or ion makes available a number empty s, p and d atomic
orbitals equal to its coordination number. These vacant orbitals hybridized together to
form hybrid orbitals which are the same in number as the atomic orbitals hybridized
together. These hybrid orbitals are vacant, equivalent in energy and have definite
geometry: Important types of hybridisation occuring in the first row transition metal (3d)
complexes and the geometry of the complex are given in Table.

2. The ligands have at least one ?-orbital containing a lone pair of electrons.

3. Vacant hybrid orbitals of the metal atom or ion overlap with the filled (containing lone
pair of electrons) ?-orbitals of the ligands to form ligand→ metal ?-bond. This bond is
known as coordinate bond is a special type of covalent bond and shows the
characteristics of both the overlapping orbitals. However, it also possesses a
considerable amount of polarity because of the mode of its formation.

4. The non-bonding electrons of the metal atom or ion are rearranged in the metal
orbitals (viz. pure d, s or p orbitals as the case may be) which do not participate in
forming the hybrid orbitals. The rearrangement of non-bonding electrons takes place
according to Hund's rule.

Q.Different octahedral square planar and tetrahedral complexes of Cr, Fe, Co, Ni,
Cu and Zn,

Here's a more comprehensive breakdown of the possible geometries for Cr, Fe, Co, Ni,
Cu, and Zn, considering the interplay between d-electron configuration, Crystal Field
Splitting (CFS), and ligand characteristics:

Chromium (Cr):

Cr(III): With a d³ configuration, chromium(III) has an odd number of electrons and

experiences minimal electron-electron repulsion. Therefore, it forms stable octahedral
complexes to maximize the distance between the d-orbitals and the ligands. This
minimizes the energy difference caused by CFS. A common example is Chromium(III)
chloride (CrCl₃), where six chloride ions surround the central Cr(III) ion in an octahedral
arrangement.

Iron (Fe):

Fe(II): Iron(II) with a d⁶ configuration can exhibit more flexibility in geometry. Strong field
ligands, which donate a large amount of electrons to the metal center, create a
significant energy gap between the t₂g and eg orbitals due to CFS. This favors an
octahedral geometry because it minimizes the number of electrons placed in the
higher-energy eg orbitals. An example is Iron(II) chloride tetrahydrate (FeCl₄²⁻), where
four chloride ions surround the Fe(II) in an octahedral shape within a complex ion.

In contrast, weaker field ligands donate fewer electrons, resulting in a smaller energy
gap between the orbitals. This can lead to tetrahedral geometry for Fe(II) to avoid
placing extra electrons in the eg orbitals altogether. Iron(II) chloride with tetrahydrofuran
(FeCl₂(THF)₂) exemplifies this, where two chloride and two tetrahydrofuran (THF)
ligands form a tetrahedral arrangement around the Fe(II) ion.
Fe(III): Similar to Cr(III), Fe(III) (d⁵) has an electronic configuration that favors octahedral
complexes. The loss of an electron from Fe(II) leaves it with five d-electrons, again
minimizing electron-electron repulsion in an octahedral geometry.

Cobalt (Co):

Co(II): Cobalt(II) possesses a d⁷ configuration. In the free ion state, the electrons occupy
all five t₂g orbitals and start filling the higher-energy eg orbitals. However, in an
octahedral complex, the CFS creates a larger energy gap between these sets. To
minimize the energy penalty, Co(II) adopts an octahedral geometry where the extra
electron goes into one of the eg orbitals, leading to a high-spin configuration with four
unpaired electrons. This is observed in Cobalt(II) chloride hexahydrate (CoCl₂•6H₂O)

Nickel (Ni):

Ni(II): With a d⁸ configuration, Nickel(II) has all five t₂g orbitals filled and starts filling the
eg orbitals. In an octahedral complex, this would force two electrons into the eg orbitals.
However, square planar geometry offers an alternative. By arranging four ligands in a
square plane, the eg orbitals experience less repulsion from the ligands, allowing all
eight electrons to occupy the lower-energy t₂g orbitals in the complex. This explains the
prevalence of square planar geometry for Ni(II) complexes like Nickel(II) carbonyl
(Ni(CO)₄).

However, ligand size can play a role. Bulky ligands might create steric hindrance in a
square planar arrangement, leading to a more spacious tetrahedral geometry in some
cases. Nickel(II) chloride (NiCl₄²⁻) exemplifies this, where the four chloride ions occupy a
tetrahedral arrangement around the central Ni(II) ion.

Copper (Cu):

Cu(I): Copper(I) has a completely filled d-shell (d¹⁰). It doesn't exhibit the same
preference for specific geometries based on electron repulsion. However, the size and
shape of the ligands can influence the arrangement. Linear or tetrahedral geometries
are common for Cu(I) complexes depending on the ligand. Copper(I) chloride (CuCl) is
an example of a tetrahedral Cu(I) complex.

Q.Strength of ligands and stability of complexes.

The strength of a ligand and the stability of a complex are closely linked. A ligand is an atom or
molecule that binds to a central metal ion in a coordination compound. The strength of this
binding interaction determines how stable the complex is. Stronger ligand-metal bonds lead to
more stable complexes.

Here are some factors that affect the strength of ligands and the stability of complexes:

● Basicity of the ligand: Lewis basicity refers to a ligand's ability to donate an electron pair to
a metal ion. Stronger Lewis bases, which can donate electrons more readily, form more
 stable complexes with metal ions. For example, ammonia (NH3) is a stronger Lewis base
than water (H2O), so it forms more stable complexes with metal ions.

● Charge on the central metal ion: Cations with higher charges can attract electrons from
ligands more strongly, leading to more stable complexes.
● Size of the metal ion: For ligands of similar size, a larger metal ion can interact with more
orbitals on the ligand, resulting in a stronger bond and a more stable complex.
● Nature of the metal-ligand bond: The more covalent character a bond has, the stronger it
will be. This is because covalent bonds involve the sharing of electrons between the metal
and the ligand.
● Chelate effect: A chelating ligand is a ligand that can bond to a metal ion at two or more
sites. Chelation increases the stability of a complex because it creates a more rigid structure
and reduces the entropy of the system.

● Steric effects: Bulky groups on a ligand can create steric hindrance, which can interfere with
the formation of strong bonds between the ligand and the metal ion. This can decrease the
stability of the complex.

Q.HS and LS complexes.

High spin (HS) and low spin (LS) complexes are distinct electronic configurations observed in
transition metal complexes. These configurations arise from a competition between two
energetic forces:

● Crystal Field Splitting Energy (CFSE): This originates from the repulsion between the
d-electrons in the central metal ion and the electrons from the surrounding ligands. The
specific geometry of the complex dictates how the d-orbitals split into higher and lower
energy levels. For instance, octahedral and tetrahedral geometries cause a smaller CFSE
compared to square planar arrangements.
● Electron Pairing Energy: This represents the energy required to force two electrons with
opposite spins to occupy the same orbital. Electrons naturally prefer to be unpaired, following
Hund's Rule of maximum spin multiplicity.

High Spin (HS) Complexes:

● When the CFSE is insufficient to overcome the electron pairing energy, the complex adopts
a high spin configuration. In this scenario, it's energetically more favorable to keep the
electrons unpaired even if it means occupying higher energy d-orbitals.
● This configuration results in complexes with a greater number of unpaired electrons,
leading to higher spin multiplicities (a measure of the total spin).
● HS complexes are typically observed in octahedral and tetrahedral geometries. In these
geometries, the d-orbitals experience a smaller CFSE due to a smaller energy gap between
them. This makes it less favorable to pair up electrons compared to placing them in these
higher energy orbitals.

Low Spin (LS) Complexes:

● Conversely, when the CFSE is larger than the electron pairing energy, the complex favors a
 low spin configuration. Here, overcoming the repulsion between electrons becomes
energetically more favorable compared to placing them in higher energy d-orbitals.
● Electrons strategically pair up in the lower energy d-orbitals, leading to complexes with
fewer unpaired electrons and consequently lower spin multiplicities.
● LS complexes are more prevalent in square planar geometries. The arrangement of ligands
in this geometry forces a larger energy gap between the d-orbitals, resulting in a significant
CFSE. This significant CFSE effectively overcomes the electron pairing energy, prompting
the electrons to pair up.

Predicting whether a complex will exhibit HS or LS behavior requires considering several

factors:
● The metal ion: Different metals have varying numbers of d-electrons which can influence the
pairing tendency.
● The d-electron configuration: The specific arrangement of electrons in the d-orbitals plays
a role in determining the pairing preference.
● The geometry of the complex: As discussed, the geometry dictates the magnitude of the
CFSE.
● The nature of the ligands: Ligands with strong electron-withdrawing capabilities can cause
a larger CFSE, favoring LS complexes.

The Valence Bond Theory’s Limitations

1. While it provides a qualitative depiction of the complex, it does not provide a
quantitative interpretation of the complex’s stability.
2. It does not account for the complexes spectra (colour).
3. It predicts no distortion in symmetrical compounds, but predicts distortion in all
copper (II) and titanium (III) complexes.
4. It provides no specific information regarding the complexes’ magnetic
characteristics. It cannot, for example, account for the complexes’
temperature-dependent paramagnetism.
5. It does not explain why, at times, the electrons must be placed in contravention of
Hund’s rule, while at other times, the electrical configuration remains unaltered.
6. It fails to account satisfactorily for the occurrence of inner and outer orbital
complexes.
7. Occasionally, the theory requires electrons to be transferred from a lower energy
level (Example 3d) to a higher energy level (4p), which is highly implausible in
 the absence of a source of energy.
8. Electron spin resonance demonstrates that the electron is not in the 4p level in
Cu(II) complexes, indicating that the complex is planar.
9. It is unable to account for why some complexes are more labile than others.
Complexes that are labile are those in which one ligand can be easily displaced
by another. Inert complexes, on the other hand, are ones in which ligand
displacement is sluggish

Crystal Field Theory

A major feature of transition metals is their tendency to form complexes. A complex may
be considered as consisting of a central metal atom or ion surrounded by a number of
ligands. The interaction between these ligands with the central metal atom or ion
is subject to crystal field theory.

Crystal field theory was established in 1929 and treats the interaction of metal ion and
ligand as a purely electrostatic phenomenon where the ligands are considered as point
charges in the vicinity of the atomic orbitals of the central atom. Development and
extension of crystal field theory taken into account the partly covalent nature of bonds
between the ligand and metal atom mainly through the application of molecular orbital
theory. Crystal field theory is often termed ligand field theory.

Overview of Crystal Field Theory

In order to understand clearly the crystal field interactions in transition metal complexes,
it is necessary to have knowledge of the geometrical or spatial disposition of d orbitals.
The d-orbitals are fivefold degenerate in a free gaseous metal ion. If a spherically
symmetric field of negative ligand filed charge is imposed on a central metal ion, the
d-orbitals will remain degenerate but followed by some changes in the energy of the
free ion. Crystal field theory was proposed which described the metal-ligand bond as
an ionic bond arising purely from the electrostatic interactions between the metal ions
and ligands. Crystal field theory considers anions as point charges and neutral
molecules as dipoles.When transition metals are not bonded to any ligand, their d
orbitals degenerate that is they have the same energy. When they start bonding with
other ligands, due to different symmetries of the d orbitals and the inductive effect of the
ligands on the electrons, the d orbitals split apart and become non-degenerate. A
summary of the interactions is given below.
Crystal Field Splitting in Octahedral Complex

In the case of an octahedral coordination compound having six ligands surrounding the metal
atom/ion, we observe repulsion between the electrons in d orbitals and ligand electrons.
This repulsion is experienced more in the case of dx2-y2 and dz2 orbitals as they point towards
the axes along the direction of the ligand. Hence, they have higher energy than average energy
in the spherical crystal field. On the other hand, dxy, dyz, and dxz orbitals experience lower
repulsions as they are directed between the axes. Hence, these three orbitals have less energy
than the average energy in the spherical crystal field.

Thus, the repulsions in octahedral coordination compound yield two energy levels:

● t2g– set of three orbitals (dxy, dyz and dxz) with lower energy
● eg – set of two orbitals (dx2-y2 and dz2) with higher energy
This splitting of degenerate level in the presence of ligand is known as crystal field splitting.
The difference between the energy of t2g and eg level is denoted by “Δo” (subscript o stands for
octahedral). Some ligands tend to produce strong fields thereby causing large crystal field
splitting whereas some ligands tend to produce weak fields thereby causing small crystal field
splitting.

Crystal Field Splitting in Tetrahedral Complex

The splitting of fivefold degenerate d orbitals of the metal ion into two levels in a
tetrahedral crystal field is the representation of two sets of orbitals as Td. The electrons
in dx2-y2 and dz2 orbitals are less repelled by the ligands than the electrons present in
dxy, dyz, and dxz orbitals. As a result, the energy of dxy, dyz, and dxz orbital sets are
raised while that of the dx2-y2 and dz2 orbitals are lowered.

● There are only four ligands in Td complexes and therefore the total negative
charge of four ligands and hence the ligand field is less than that of six ligands.
● The direction of the orbitals does not coincide with the directions of the ligands
approach to the metal ion.
Thus, the repulsions in tetrahedral coordination compound yield two energy levels:

● t2– set of three orbitals (dxy, dyz and dxz) with higher energy
● e – set of two orbitals (dx2-y2 and dz2) with lower energy

The crystal field splitting in a tetrahedral complex is intrinsically smaller in an octahedral

filed because there are only two thirds as many ligands and they have a less direct
effect of the d orbitals.

Square Planar Complexes

The other common geometry is square planar. It is possible to consider a square planar
geometry as an octahedral structure with a pair of trans ligands removed. The removed
ligands are assumed to be on the z-axis. This changes the distribution of the d orbitals,
as orbitals on or near the z-axis become more stable, and those on or near the x- or
y-axes become less stable. This results in the octahedral t2g and the eg sets splitting
and gives a more complicated splitting pattern (Figure 2).
High Spin and Low Spin
The complexion with the greater number of unpaired electrons is known as the high spin
complex, the low spin complex contains the lesser number of unpaired electrons. High
spin complexes are expected with weak field ligands whereas the crystal field splitting
energy is small Δ. The opposite applies to the low spin complexes in which strong field
ligands cause maximum pairing of electrons in the set of three t2 atomic orbitals due to
large Δo.

● High spin – Maximum number of unpaired electrons.

● Low spin – Minimum number of unpaired electrons.

Example: [Co(CN)6]3- & [CoF6]3-

● [Co(CN)6]3- – Low spin complex

● [CoF6]3- – High spin complex
Q.Factors Affecting Octahedral Splitting Energy (Δo

The magnitude of octahedral splitting energy (Δo) plays a key role in understanding the
properties of coordination complexes. Here are the main factors that affect Δo:

1. **Nature of the Ligand:** This is often considered the most crucial factor. Ligands
are categorized based on their ability to donate electrons to the metal center. Stronger
field ligands, like CN-, F-, or CO, cause a larger Δo due to their greater attraction to the
metal d-orbitals. This is often referred to as the spectrochemical series, which ranks
ligands according to their field strength. Weaker field ligands, like I- or Cl-, result in a
smaller Δo.

2. **Oxidation State of the Metal Ion:** Metal ions with higher charges (increased
oxidation state) tend to have a larger Δo. This is because the greater positive charge
attracts the electrons in the d-orbitals more strongly, leading to a larger interaction with
the ligand electrons.

3. **Principal Quantum Number (n) of the Metal:** As you move down a group in the
periodic table (increasing n), the metal d-orbitals become more diffuse (spread out) due
to the presence of more shells. This allows for better overlap with the ligand orbitals,
leading to a generally larger Δo for elements lower in a group compared to those higher
up.

While these are the main factors, it's important to note that Δo can also be influenced
by:

* **Geometry of the Complex:** Octahedral geometry is the focus here, but other
geometries (like tetrahedral) will have different splitting patterns and magnitudes.

* **Number of d-Electrons:** The number of electrons present in the d-orbitals of the

metal can influence the filling of the t2g and eg orbitals (resulting from the splitting),
impacting the overall stability and affecting Δo to some extent.

Understanding how these factors affect Δo helps predict various properties of

coordination complexes, such as color, magnetism, and stability.

Crystal Field Stabilization Energy

In a chemical environment, the energy levels generally split as directed by the symmetry of the
local field surrounding the metal ion. The energy difference between the eg and t2g levels is
given as or 10Dq. It states that each electron that goes into the lower t2g level stabilizes the
system by an amount of -4Dq and the electron that goes into eg level destabilizes the system by
+6Dq. That is the t2g is lowered by 4Dq and the eg level is raised by +6Dq.
For example, the net change in energy for d5 and d10 systems will be zero as shown below.

d5 :- 3(-4Dq) + 2(+6Dq) = -12Dq + 12Dq = 0

d10 :- 6(-4Dq) + 4(+6Dq) = -24Dq + 24Dq = 0

The decrease in energy caused by the splitting of the energy levels is called the
“Ligand Field Stabilization Energy (LFSE)”.

Thus, the crystal field splitting depends on the field produced by the ligand and the
charge on the metal ion. An experimentally determined series based on the absorption
of light by coordination compound with different ligands known as spectrochemical
series has been proposed. Spectrochemical series arranges ligands in order of their
field strength as:

I– < Br– < Cl– < SCN– < F– < OH– < C2O42- < H2O < NCS– < EDTA4- < NH3 < en < CN–< CO

Filling of d-orbitals takes place in the following manner; the first three electrons are
arranged in t2g level as per the Hund’s rule. The fourth electron can either enter into the
t2g level giving a configuration of t2g4eg0 or can enter the eg orbital giving a configuration
of t2g3eg1. This depends on two parameters magnitude of crystal field splitting, Δo and
pairing energy, P. The possibilities of the two cases can better be explained as

● Δo > P – Electron enters in the t2g level giving a configuration of t2g4eg0. Ligands
producing this configuration are known as strong field ligands and form low spin
complexes.
● Δo < P – Electron enters in the eg level giving a configuration of t2g3eg1. Ligands
producing this configuration are known as weak field ligands and form high spin
complexes.
Magnetic Properties of CoordinationCompounds:-

The capacity of transition metals to create magnets is a notable property. The

coordination compound complexes show magnetic properties. Unpaired electrons in
coordination metal complexes make them magnetic in nature. This magnetism must be
owing to the presence of unpaired d electrons because the final electrons are in the d
orbitals. The electronic spin generates magnetism and the number of unpaired electrons
in a molecule determines its magnetic properties. A magnetic field is produced by the
movement of magnetic or electric charges. These magnetic field lines of force have
certain definite properties. The magnetism shown by the complexes is mainly three
types: ferromagnetism, paramagnetism and diamagnetism.
The quantum number ms represents the spin of a single electron as +(12 )or –(12 ).
When an electron is linked with another, its spin is negated, but when the electron is
unpaired, it forms a weak magnetic field. The paramagnetic effects are amplified when
there are more unpaired electrons. The repulsive forces between electrons in the
ligands and electrons in the compound cause the electron configuration of a transition
metal (d-block) to change in a coordination compound. The chemical may be
paramagnetic or diamagnetic, depending on the strength of the ligand.
The magnetic moment of a system containing unpaired electrons is proportional to the
number of unpaired electrons: the stronger the magnetic moment, the more unpaired
electrons there are. The force that a substance feels in a magnetic field is measured by
magnetic susceptibility.

Properties of magnet

● The magnet attracts ferromagnetic materials (iron)

● Magnetic poles exist in pairs in magnets, and each magnet has two magnetic
poles, N pole and S pole
 ● On suspending a magnet freely, it always comes in the north-south direction
● When two magnets are in close proximity, the same magnetic poles repel and
push away from one other, whereas different magnetic poles attract and stick to
each other
● As a result, the same poles repel each other while the opposite poles attract.

Ferromagnetism or Permanent Magnets

The fundamental mechanism by which certain materials (such as iron) produce
permanent magnets is ferromagnetism. This indicates the material has persistent
magnetic properties rather than merely expressing them when exposed to a magnetic
field from the outside. The electrons of atoms in a ferromagnetic element are organised
into domains, each with the same charge. These domains align in the presence of a
magnetic field, resulting in parallel charges over the entire complex. The number of
unpaired electrons and the atomic size of a chemical determine whether it is
ferromagnetic or not.

Paramagnetism – Attracted to the Magnetic Field

The magnetic condition of an atom having one or more unpaired electrons is known as
paramagnetism. Due to the electrons’ magnetic dipole moments, the magnetic field
attracts the unpaired electrons. Before any orbital is to be twice occupied, according to
Hund’s Rule, electrons must occupy it singly. This results in a higher number of
unpaired electrons in the atom. Unpaired electrons have magnetic properties in both
directions because they can spin in either way. Magnetic fields attract paramagnetic
atoms because of this ability. O2, or diatomic oxygen, is an excellent example of
paramagnetism (described using the molecular orbital theory).

Diamagnetism – Repelled by the Magnetic Field

The magnet has no effect on molecular nitrogen (N2) since it has no unpaired electrons
and is diamagnetic. The presence of paired electrons, i.e., no unpaired electrons,
distinguishes diamagnetic compounds. The electron spins are oriented in different
directions according to the Pauli Exclusion Principle, which stipulates that no two
electrons may occupy the same quantum state at the same moment. As a result, the
magnetic fields of the electrons cancel out, leaving no net magnetic moment and
preventing the atom from being attracted to a magnetic field.

How to Find Out the Magnetic Nature (Paramagnetic or Diamagnetic) of a

Complex?

The electron configuration of a substance can be used to identify its magnetic

properties: the substance is paramagnetic if its electrons are unpaired, and it is
diamagnetic if all of its electrons are paired. The three steps required are:

● Write the electronic configuration.

● Make a diagram of the valence orbitals.
● Determine whether the substance is paramagnetic or diamagnetic by looking for
unpaired electrons.

Conclusion

The coordination metal complexes exhibit magnetic nature due to the presence of
electrons in the d orbital, either paired or unpaired. Magnetism is mainly of three types:
paramagnetism, diamagnetism and ferromagnetism. Paramagnetism is caused due to
the presence of unpaired electrons in the d orbital and diamagnetism results due to the
fully paired electron in d orbitals. Ferromagnetism is exhibited by metal complexes that
can retain their magnetism for a longer time once magnetised. There are some
properties that a magnet exhibits, like the same poles will repel and the unlike poles will
show an attraction, and when the magnet is suspended, it will always align in the N-S
direction.

Colour of Complexes:-
Colour of complexes has a wide range, i.e. compounds can either have a very pale
colour or a very intense one. Various factors determine this

One of the most remarkable properties of coordination compounds is the wide range of
colours shown by them. It has been a subject of great interest to chemists. Why is it that
the hexaaquairon(II) complex appears red, but the hexaaquacobalt(II) complex appears
pink and hexaaquanickel(II) complex green? The answer to such questions lies in the
crystal field theory of coordination compounds. However, before we learn that, it is
crucial to understand why we see colours in the first place. We see the colour in any
compound whenever it absorbs visible radiation.

Colour Wheel

You must be aware of the electromagnetic radiation spectrum CGXUVIMR in which

radiations are placed in the order of increasing wavelength or decreasing frequency.
Whenever light of varying wavelengths is incident on a sample, the sample absorbs
radiation of a particular range of wavelengths only. If it absorbs radiation in the visible
range, then we see colour complementary to the colour it absorbs.

Colour of Complexes Meaning:-

The colour of complexes is because of electronic transitions between different energy

levels. The transition occurs from one d-orbital to another d-orbital. But how is it
possible if all the d-orbitals are equal in energy, i.e., degenerate? d-orbitals of metal are
indeed degenerate. However, their energy changes when they come in the vicinity of a
ligand.

This can be explained by the crystal field theory (CFT). CFT states that bonding
between metal and ligand occurs purely out of electrostatic interactions between the
two. As per this, we treat ligands as point charges in the case of anions and point
dipoles in the case of neutral molecules. Due to these point charges/dipoles, the
degeneracy of the d-orbitals is lost. They split into two different sets of orbitals having
different energies. This splitting happens differently in octahedral and tetrahedral
complexes.

Conclusion

We discussed why we could see colours in real life in this colour of complex notes. In
coordination compounds, colour arises because of d-d electronic transitions. This can
be explained by the crystal field theory. To understand the colour of complexes
meaning, getting a hold on CFT is crucial. CFT happens differently in octahedral and
tetrahedral complexes. Understanding the spectrochemical series of ligands is
important to understand the differences in the colour of compounds. LMCT can give
colours in compounds where d-d electronic transitions are not possible.

Variation of Octahedral Ionic Radii in Spinels:-

The variation of octahedral ionic radii in spinels is an important factor influencing their
physical and chemical properties. Spinels are a class of compounds with the general
formula AB2O4, where A and B are cations and O is oxygen. The crystal structure of
spinels can be described as a close-packed arrangement of oxide ions (O2-) with
cations occupying two distinct types of interstitial sites:

● Tetrahedral sites: These are smaller voids coordinated by four oxygen ions
arranged in a tetrahedral shape.
● Octahedral sites: These are larger voids coordinated by six oxygen ions arranged in
an octahedral shape.

The specific cations occupy these sites depending on their size and charge. The radius
of the cation occupying the octahedral site (r octahedral) can vary significantly
depending on the specific element. Here's a general trend:

● Larger cations tend to favor the octahedral sites due to a better size fit.
● Smaller cations may occupy either tetrahedral or octahedral sites depending on the
charge balance and other factors.

The variation in octahedral ionic radii can affect properties like:

● Lattice parameter: The overall size of the unit cell in the spinel structure is
influenced by the size of the cations in the octahedral sites.
● Electrical conductivity: The mobility of ions within the spinel lattice can be affected
by the size and charge of the cations.
● Magnetic properties: In many spinel oxides, the magnetic behavior is determined by
the interactions between cations in the octahedral sites.
Crystal Structure of Spinels

Spinels crystallize in the cubic crystal system with a space group Fd-3m. The unit cell of
a spinel can be visualized as a face-centered cubic (FCC) arrangement of oxide ions
with cations occupying tetrahedral and octahedral sites as described earlier. Here's a
breakdown of the structure:

● Eight oxide ions (O2-): These occupy the corners and face centers of the unit cell.
● Four cations (A-site): These occupy the tetrahedral sites formed by four oxygen
ions.
● Six cations (B-site): These occupy the octahedral sites formed by six oxygen ions.

![[Crystal structure of spinel]]

The specific occupancy of A and B sites by cations depends on the type of spinel. There
are two main types of spinel structures based on cation distribution:

● Normal spinel: In this type, the A sites are occupied by divalent cations (2+ charge),
and the B sites are occupied by trivalent cations (3+ charge). An example is
MgAl2O4 (magnesium aluminate).
● Inverse spinel: In this type, some of the trivalent cations from B sites move to
occupy the A sites along with the divalent cations. The remaining B sites are then
filled by a mix of divalent and trivalent cations, depending on the specific compound.
An example is Fe3O4 (magnetite).

The understanding of variations in octahedral ionic radii and crystal structure is crucial
for researchers and engineers designing new spinel materials with tailored properties
for applications in catalysis, electronics, magnetism, and energy storage.

Jahn-Teller Distortions
The Jahn-Teller effect is a geometric distortion of a non-linear molecular system that
reduces its symmetry and energy. This

distortion is typically observed among octahedral complexes where the two axial bonds
can be shorter or longer than those of the

equatorial bonds. This effect can also be observed in tetrahedral compounds. This
effect is dependent on the electronic state of the system.
Introduction

In 1937, Hermann Jahn and Edward Teller postulated a theorem stating that "stability
and degeneracy are not possible

simultaneously unless the molecule is a linear one," in regards to its electronic state.[1]
This leads to a break in degeneracy which

stabilizes the molecule and by consequence, reduces its symmetry. Since 1937, the
theorem has been revised which Housecroft and

Sharpe have eloquently phrased as "any non-linear molecular system in a degenerate

electronic state will be unstable and will

undergo distortion to form a system of lower symmetry and lower energy, thereby
removing the degeneracy."[2] This is most

commonly observed with transition metal octahedral complexes, however, it can be

observed in tetrahedral compounds as well.

For a given octahedral complex, the five d atomic orbitals are split into two degenerate
sets when constructing a molecular orbital

diagram. These are represented by the sets' symmetry labels: ( , , ) and ( and ). When a
molecule

possesses a degenerate electronic ground state, it will distort to remove the degeneracy
and form a lower energy (and by

consequence, lower symmetry) system. The octahedral complex will either elongate or
compress the ligand bonds as shown in Figure below:1

Figure : Jahn-Teller distortions for an octahedral complex.

When an octahedral complex exhibits elongation, the axial bonds are longer than the
equatorial bonds. For a compression, it is the

reverse; the equatorial bonds are longer than the axial bonds. Elongation and
compression effects are dictated by the amount of

overlap between the metal and ligand orbitals. Thus, this distortion varies greatly
depending on the type of metal and ligands. In

general, the stronger the metal-ligand orbital interactions are, the greater the chance for
a Jahn-Teller effect to be observed.
Elongation

Elongation Jahn-Teller distortions occur when the degeneracy is broken by the

stabilization (lowering in energy) of the d orbitals

with a z component, while the orbitals without a z component are destabilized (higher in
energy) as shown in Figure below:2

This is due to the dxy

and dx2−y2

orbitals having greater overlap with the ligand orbitals, resulting in the orbitals being
higher in energy. Since the dx2−y2

orbital is antibonding, it is expected to increase in energy due to elongation. The dxy

orbital is still nonbonding, but is destabilized due to the interactions. Jahn-Teller

elongations are well-documented for copper(II) octahedral compounds. A classic
example is that of copper(II) fluoride as shown in Figure- 3

Notice that the two axial bonds are both elongated and the four shorter equatorial bonds
are the same length as each other. According the theorem, the orbital degeneracy is
eliminated by distortion, making the molecule more stable based on the model
presented in figure -2

Compression

Compression Jahn-Teller distortions occur when the degeneracy is broken by the

stabilization (lowering in energy) of the d orbitals without a z component, while the
orbitals with a z component are destabilized (higher in energy).

This is due to the z-component d orbitals having greater overlap with the ligand orbitals,
resulting in the orbitals being higher in energy. Since the dz2 orbital is antibonding, it is
expected to increase in energy due to compression. The dxz and dyz orbitals are still
nonbonding, but are destabilized due to the interactions.

Electronic Configurations

For Jahn-Teller effects to occur in transition metals there must be degeneracy in either
the t2g or e.g. orbitals. The electronic states of octahedral complexes depend on the
number of d-electrons and the splitting energy, Δ

. When Δ

is large and is greater than the energy required to pair electrons, electrons pair in t2g
before occupying eg. On the other hand, when Delta
 small and is less than the pairing energy, electrons will occupy eg before pairing in t2g.
The Δ

of an octahedral complex is dictated by the chemical environment (ligand identity), and

the identity and charge of the metal ion. If there electron configurations for any
d-electron count is different depending on Δ

, the configuration with more paired electrons is called low spin while the one with more
unpaired electrons is called high spin.

The electron configurations diagrams for d1 through d10 with large and small δ

are illustrated in the figures below. Notice that the electron configurations for d1, d2,
d3, d8, d9, and d10 are the same no matter what the magnitude of Δ

. Low spin and high spin configurations exist only for the electron counts d4, d5, d6,
and d7.

Spectroscopic Observation

Jahn-Teller distortions can be observed using a variety of spectroscopic techniques. In

UV-VIS absorption spectroscopy, distortion causes splitting of bands in the spectrum
due to a reduction in symmetry (Oh to D4h). Consider a hypothetical molecule with
octahedral symmetry showing a single absorption band. If the molecule were to undergo
Jahn-Teller distortion, the number of bands would increases.

A similar phenomenon can be seen with IR and Raman vibrational spectroscopy. The
number of vibrational modes for a molecule can be calculated using the 3n - 6 rule (or
3n - 5 for linear geometry) rule. If a molecule exhibits an Oh symmetry point group, it will
have fewer bands than that of a Jahn-Teller distorted molecule with D4h symmetry.
Thus, one could observe Jahn-Teller effects through either IR or Raman techniques.
This effect can also be observed in EPR experiments as long as there is at least one
unpaired electron.

The Jahn-Teller Theorem predicts that distortions should occur for any degenerate
state, including degeneracy of the t2g level, however distortions in bond lengths are
much more distinctive when the degenerate electrons are in the eg level .
.Figure - 3 copper(II) fluoride as shown.

Figure:-1 Figure : Jahn-Teller distortions for an octahedral complex

Figure:-2Illustration of tetragonal distortion (elongation) for an octahedral
complex.
Charge-Transfer Spectra

Figure 11.3.7.1 : Some examples of complexes with d0 and d10 electron

configurations, and their colors. Attribution: E.R. Schofield.

Charge transfer spectra are a type of electronic spectroscopy that can be used to study
the transfer of electrons between molecules or atoms. In the context of transition
metals, charge transfer spectra are often used to study the transfer of electrons
between the metal ion and its ligands.There are two main types of charge transfer
spectra: ligand-to-metal charge transfer (LMCT) and metal-to-ligand charge transfer
(MLCT).
 ● LMCT spectra occur when an electron is transferred from a ligand to a metal ion.
This can occur when the ligand is a donor, such as a halide ion or an amine.
LMCT spectra are typically broad and featureless, but they can provide
information about the energy of the lowest unoccupied molecular orbital (LUMO)
of the metal ion.
● MLCT spectra occur when an electron is transferred from a metal ion to a ligand.
This can occur when the ligand is an acceptor, such as a nitro group or a cyano
group. MLCT spectra are typically sharper and more intense than LMCT spectra,
and they can provide information about the energy of the highest occupied
molecular orbital (HOMO) of the metal ion.

Figure 11.3.7.2 : Charge-transfer transitions. Attribution: E.R. Schofield.

The explanation for these phenomena is charge-transfer transitions ( 11.3.7.2) There
are two types of charge-transfer transitions: ligand-to-metal (LMCT) and metal-to-ligand
(MLCT) charge transfer transitions. For the ligand-to-metal transitions, electrons from
bonding σ and π-orbitals get excited into metal d-orbitals in the ligand field, for example
the t2g and the eg orbitals in an octahedral complex. If the energy difference between
the σ/π-orbitals and the d-orbitals is small enough, then this electron transition is
associated with the absorption of visible light. The transition is called a ligand-to-metal
transition because the ligand σ/π-orbitals are mostly located at the ligands, while the
metal-d-orbitals in a ligand field are mostly located at the metal. Vice versa, the
metal-to-ligand transition involves the transition of an electron from metal d-orbitals in a
ligand field to ligand π*-orbitals. This essentially moves electron density from the metal
to the ligand, hence the name ligand-to-metal-charge transfer transition. If the
energy-difference between the ligand π* and the metal orbitals is small enough, then
the absorption occurs in the visible range. Charge-transfer transitions are usually both
spin- and Laporte allowed; hence, if they occur, the color is often very intense. How can
we distinguish between d-d and charge transfer transitions? Charge transfer transitions
often change in energy as the solvent polarity is varied (solvatochromic), as there is a
change in polarity of the complex associated with the charge transfer transition. This
can be used to distinguish between d-d transitions and charge-transfer bands.

LMCT Transitions
Can we predict when the energy windows between the bonding molecular orbitals and
the metal d-orbitals are small enough for LMCT transitions in the visible to take place?
Generally, it would be desirable if the energy of the metal orbitals were as low as
possible and the energy of the bonding ligand orbitals were as high as possible. The
energy of metal d-orbitals decreases with increasing positive charge at the metal
because the effective nuclear charge on the metal increases. This means that very high
metal oxidation states favor LMCT transitions. The d-orbitals should have few or no
electrons, so that electrons can be promoted into the orbitals, and orbital energy
decreases because electron-electron repulsion is minimized. Examples are Mn(VII),
Cr(VI), and Ti(IV). The energy of MOs from bonding ligand orbitals increases when the
ligand orbitals have high energy; this is typically the case for π-donor ligands with a
negative charge (Fig. 8.2.21).The properties of the metal ions and ligands suitable for
LMCT transitions. MnO4- is deep purple due to LMCT transitions.

Examples of ligands are oxo- and halo ligands. This explains, for example, the LMCT
transitions in permanganate. The Mn is in the very high oxidation state +7, and the
ligands are oxo-ligands, which are π-donors with a 2- negative charge. The transitions
are both Laporte and spin-allowed, leading to a very high intensity of light absorption,
and thus color.
MLCT Transitions
What are favorable metal ion and ligand properties for a metal-to-ligand transition, then?
In this case we would like to keep the energy of the metal orbitals as high as possible so
that the energy difference between a metal d-orbital and a π*-orbital is minimized. This
is accomplished when the positive charge at the metal ion is small, and there are many
d-electrons that can repel each other, thereby increasing orbital energies, for example
Cu(I),The ligand should be a π-acceptor with low-lying π*-orbitals - for example,
phenanthroline, CN-, SCN-, and CO. The bis(phenanthroline) copper(+) ion, for
instance, is dark orange and has an MLCT absorption band at 458 nm. This MLCT
transfer is both spin and Laporte-allowed.

It should be mentioned that some complexes allow for both metal-to-ligand and
ligand-to-metal transitions. For example, in the Cr(CO)6 complex, the σ-orbitals are high
enough and the π*-orbitals are low enough in energy to allow for light absorption in the
visible range. Finally, intraligand bands are also possible when the ligand is a
chromophore.

Heat of hydration :
The heat of hydration is the enthalpy change that occurs when an ion is dissolved in
water. It is a measure of the strength of the interaction between the ion and the water
molecules. The heat of hydration of bivalent metal ions of transition metals is generally
positive, which means that the process is endothermic. This is because the interaction
between the metal ion and the water molecules is stronger than the interactions
between the individual water molecules. The heat of hydration of a metal ion depends
on a number of factors, including the size of the ion, the charge of the ion, and the
polarizability of the ion. Larger ions, more highly charged ions, and more polarizable
ions tend to have larger heats of hydration.

Lattice energy:

Lattice energy is the energy required to break up one mole of a solid ionic compound
into its gaseous ions. It is a measure of the strength of the electrostatic attraction
between the positive and negative ions in the crystal lattice.

The lattice energy of bivalent metal ions of transition metals is generally high, which
means that the crystal lattices of these compounds are very stable. This is because the
metal ions are small and highly charged, and they polarize the anions to a great extent.
The lattice energy of a metal ion depends on a number of factors, including the size of
the ion, the charge of the ion, and the polarizability of the ion. Smaller ions, more highly
charged ions, and more polarizable ions tend to have higher lattice energies.
Magnetic Classification of MaterialsAll substances show some kind of
magnetic behavior. After all, they are made up of charged particles:
electrons and protons. It is the way in which electron clouds arrange
themselves in atoms and how groups of these atoms behave that
determines the magnetic properties of the material. The atom (or group of
atoms) in effect becomes a magnetic dipole or a mini bar magnet that can
align according to the magnetic field applied. The net effect of all these
dipoles determines the magnetic properties of the magnetic materials.

The two most common types of magnetism are diamagnetism and

paramagnetism, which account for most of the periodic table of elements at
room temperature. These elements are usually referred to as
non-magnetic, whereas those which are referred to as magnetic are
actually classified as ferromagnetic. The only other type of magnetism
observed in pure elements at room temperature is antiferromagnetism.
Finally, magnetic materials can also be classified as ferrimagnetic although
this is not observed in any pure element but can only be found in
compounds, such as the mixed oxides, known as ferrites, from which
ferrimagnetism derives its name. The value of magnetic susceptible falls
into a particular range for each type of material .

Diamagnetism

In a diamagnetic material the atoms have no net magnetic moment when

there is no applied field. Under the influence of an applied field (H) the
spinning electrons precess and this motion, which is a type of electric
current, produces a magnetisation (M) in the opposite direction to that of
the applied field. All materials have a diamagnetic effect, however, it is
often the case that the diamagnetic effect is masked by the larger
paramagnetic or ferromagnetic term. The value of susceptibility is
independent of temperature.

Paramagnetism

In these materials, the magnetic dipoles in the magnetic materials tend to

align along the applied magnetic field and thus reinforcing the applied
magnetic field. Such substances are attracted by a magnet if it applies a
sufficiently strong field. It must be noted that such materials are still feeble
magnetized and the magnetisation disappears as soon as the external field
is removed. The magnetisation (M) of such materials was discovered by
Madam Curie and is dependent on the external magnetic field (B) and
temperature T as:

M = C B/T

Where C= Curie Constant

Ex: Liquid oxygen, sodium, platinum, salts of iron and nickel.

Ferromagnetic materials

We are most familiar with these materials as they exhibit the strongest
magnetic behaviour. Magnetic dipoles in these materials are arranged into
domains where the arrangements of individual magnetic dipoles are
essentially perfect that can produce strong magnetic fields. Normally, these
domains are usually randomly arranged and thus the magnetic field of each
domain is cancelled by another and the entire material does not show any
magnetic behaviour.

However, when an external field is applied, the domains reorient

themselves to reinforce the external field and produce a strong internal
magnetic field that is along the external field. Upon removal of the external
field, most of the domains stay put and continue to be aligned in the
direction of the (erstwhile) magnetic field. Thus, the magnetic field of the
magnetic materials persists even when the external field disappears. This
property is used to produce Permanent magnets that we use every day.
Iron, cobalt, nickel, neodymium and their alloys are usually highly
ferromagnetic and are used to make permanent magnets.

Antiferromagnetism

In the periodic table the only element exhibiting antiferromagnetism at room

temperature is chromium. Antiferromagnetic materials are very similar to
ferromagnetic materials but the exchange interaction between neighbouring
atoms leads to the anti-parallel alignment of the atomic magnetic moments.
Therefore, the magnetic field cancels out and the material appears to
behave in the same way as a paramagnetic material. Like ferromagnetic
materials these materials become paramagnetic above a transition
temperature, known as the Néel temperature, TN. (Cr: TN=37ºC).
Ferrimagnetism

Ferrimagnetism is only observed in compounds, which have more complex

crystal structures than pure elements. Within these materials the exchange
interactions lead to parallel alignment of atoms in some of the crystal sites
and anti-parallel alignment of others. The material breaks down into
magnetic domains, just like a ferromagnetic material and the magnetic
behaviour is also very similar, although ferrimagnetic materials usually have
lower saturation magnetisations. For example in Barium ferrite
(BaO.6Fe2O3) the unit cell contains 64 ions of which the barium and
oxygen ions have no magnetic moment, 16 Fe3+ ions have moments
aligned parallel and 8 Fe3+ aligned antiparallel giving a net magnetisation
parallel to the applied field, but with a relatively low magnitude as only ⅛ of
the ions contribute to the magnetisation of the material.

Determination of Magnetic susceptibility

The magnetic susceptibility measures the strength of interaction on placing

the substance in a magnetic field. For chemical applications the molar
magnetic susceptibility ( χmol) is the preferred quantity and is measured in
m3·mol−1 (SI) or cm3·mol−1 (CGS) and is defined as

χmol=Mχv/ρ(20.10.1)

where ρ is the density in kg·m−3 (SI) or g·cm−3 (CGS) and M is molar

mass in kg·mol−1 (SI) or g·mol−1 (CGS). There are multiple methods for
measuring magnetic susceptibilities, including, the Gouy, Evans, and
Faraday methods. These all depend on measuring the force exerted upon
a sample when it is placed in a magnetic field. The more paramagnetic the
sample, the more strongly it will be drawn toward the more intense part of
the field.

The GOUY Method

Perhaps the simplest technique for measuring the magnetic susceptibility of

metal complexes is the Gouy Method. From a classical description of
magnetism, Lenz's Law (around 1834) can be written as

BH=1+4π I/H(4.14.4.1) or BH=1+4πκ(4.14.4.2)

where

B/H is called the magnetic permeability of the material and

κ is the magnetic susceptibility per unit volume, (I/H).

The determination of a magnetic susceptibility depends on the

measurement of B/H. Experimentally the Gouy method involves measuring
the force on the sample by a magnetic field and is dependent on the
tendency of a sample to concentrate a magnetic field within itself.

At any given point, dx, of the sample, the force is given by:

dF=μ°HκdV(dH)/dx(4.14.4.3)

where

μ° is the permeability of a vacuum (=1 when using c.g.s. units)

H is the magnitude of the magnetic field at point, dx,

dV is the volume of the sample at point dx,

κ is the magnetic susceptibility per unit volume.

L-S coupling
L-S coupling or Russell-Saunders coupling predicts results in good

agreement with the observed spectral details for many light atoms. In such

cases of multi-electron atoms the spin-orbit coupling is weak. In this

coupling scheme it is presumed that the orbital angular momenta of the

individual electrons add to form a resultant orbital angular momentum L.

Similarly, the individual spin angular momenta should couple to produce a

resultant spin angular momentum S. Then L and S combine to form the
total angular momentum.

This scheme of coupling may be visualized in terms of a vector model of

angular momentum.

J=L+S

Orbit-Orbit Interaction

Consider orbital motion of two electrons, ℓ 1 and ℓ 2 are their quantum

numbers, ℓ 1*h/2π and ℓ 2* are

their angular momenta. ℓ 1* and ℓ 2* are quantized with respect to each

other in such a way that they

form resultant

L* where L*=[L(L+1)]1/2 and

L=0, 1, 2, 3, 4, 5, 6, 7,…..for S, P, D, F, G, H, I, J,…

Consider an electron in the p orbit and other in the d orbit. Here two vectors
ℓ 1*=√2 and ℓ 2*=√6 may

orient themselves in any one of three positions L*= √2, √6 and √12
corresponding to L=1, 2, 3 or P, D, F terms. All integral values of L from ℓ 2-
ℓ 1 to ℓ 2+ ℓ 1 are allowed.

Correlation of the magnetic moment (Spin only magnetic moment):-

When electrons move around freely, they create a magnetic field; this
magnetic field created by electron motion is known as the magnetic
moment.A spin-only magnetic moment occurs when an electron rotates on
its own axis and generates a magnetic field.

The formula for the calculation of spin only magnetic moment

ūs =√n(n+3)

Here,n is the number of unpaired electrons. The unit for a spin-only

magnetic moment is the Bohr magneton (BM).

Effective magnetic moment values

Effective magnetic moment is a property of an atom, ion, or molecule that

reflects the strength of its magnetic dipole moment. It is expressed in Bohr
magnetons (BM), a unit named after Niels Bohr.

There are two main cases for calculating effective magnetic moments:

* For transition metal ions or complexes, the effective magnetic moment

(μeff) is often calculated using the spin-only formula:

μeff = √n(n + 2) BM

where n is the number of unpaired electrons in the metal ion.

* For lanthanide and actinide ions, the calculation is more complex and
involves the Lande g-factor and the total angular momentum quantum
number (J).

Here's a table showing examples of effective magnetic moment values for

some common elements and ions:

| Element/Ion | Electron Configuration | Number of Unpaired Electrons (n) |

Effective Magnetic Moment (μeff, BM) |

|---|---|---|---|

| Cu²+ | [Ar]3d⁹ | 1 | 1.73 BM |

| Fe²+ | [Ar]3d⁶ | 4 | 4.90 BM |

| Fe³⁺ | [Ar]3d⁵ | 5 | 5.92 BM |

| Gd³⁺ | [Xe]4f⁷ | 7 | 7.90 BM |

Effective magnetic moment values can be used to predict the magnetic

behavior of materials. For example, diamagnetic materials have zero or
very low effective magnetic moments, while paramagnetic materials have
positive effective magnetic moments. Ferromagnetic and antiferromagnetic
materials also have nonzero effective magnetic moments, but their
behavior is more complex.
Q.Quenching of orbital contribution to magnetic moment.

The total magnetic moment of an atom or ion comes from two sources:

1. **Spin Angular Momentum:** This is the inherent property of an

electron's spin and doesn't depend on the surrounding environment.

2. **Orbital Angular Momentum:** This arises from the motion of the

electron in its orbital.

In transition metals and their complexes, the orbital contribution to the

magnetic moment can be influenced by the surrounding ligands. This
influence is called **quenching of orbital contribution**.

Here's how it works:

* In an isolated transition metal ion, the d-orbitals are typically degenerate

(same energy). Electrons in these orbitals can move around freely. This
movement contributes to the overall orbital angular momentum.

* When ligands surround the metal ion, they create an electrostatic field
called the **crystal field**. This field interacts differently with the various
d-orbitals, splitting their energy levels.

* Due to this splitting, the degeneracy is lost. Electrons tend to occupy

lower energy orbitals.

* Depending on the specific configuration and filling of the d-orbitals, the

movement of electrons might be restricted. This restriction can cancel out
the orbital angular momentum contribution from individual electrons.

There are two main scenarios where quenching of orbital contribution

occurs:

1. **Specific Ground State Terms:** For certain electronic configurations,

the arrangement of electrons in the split d-orbitals leads to a cancellation of
the orbital angular momentum in the ground state. This is particularly true
for complexes with A or E ground state terms.

2. **Completely Filled or Half-Filled t2g orbitals:** The t2g set of

d-orbitals has a specific symmetry that allows for electron movement and
contribution to orbital angular momentum. However, if the t2g orbitals are
completely filled or half-filled with electrons, their movement becomes
symmetrical, again resulting in a cancellation of the overall orbital angular
momentum.In these cases, the effective magnetic moment of the ion or
complex is primarily determined by the spin contribution, leading to values
closer to the "spin-only" calculated values.

Applications of magnetic moment data for 3d series:-

Magnetic moment data is a powerful tool for understanding the electronic
structure and properties of 3d series transition metals and their complexes.
Here are some key applications:

**1. Determining Electronic Configuration and Oxidation State:*** The

number of unpaired electrons in a 3d metal ion directly affects its magnetic
moment. By measuring the magnetic moment, chemists can infer the
electron configuration and oxidation state of the metal center. This is
particularly useful for complex molecules where the exact structure might
not be immediately evident.

**2. Understanding Bonding and Crystal Field Effects:*** Magnetic

moment data can reveal information about the interaction between the
metal ion and the surrounding ligands in a complex. Stronger interactions
(crystal field effects) can alter the energy levels of the d-orbitals, influencing
the number of unpaired electrons and hence the magnetic moment.

**3. Distinguishing Between Spin Pairing and High/Low Spin States:***

In some cases, 3d metals can have multiple spin configurations (pairing
arrangements of electrons). Magnetic moment measurement helps
differentiate between these states. For example, a high spin Fe(II) complex
will have a higher magnetic moment compared to a low spin Fe(II) complex
due to the presence of more unpaired electrons.

**4. Studying Magnetic Materials:*** Magnetic moment data is crucial for

characterizing magnetic materials formed by 3d transition metals. It helps
determine the type of magnetism (paramagnetic, diamagnetic,
ferromagnetic) and the strength of the magnetic interaction between metal
centers.Overall, magnetic moment data provides valuable insights into the electronic
structure and bonding behavior of 3d transition metals and their complexes. This
information is essential for various fields of chemistry, including inorganic chemistry,
materials science, and catalysis.