BONDING IN COORDINATION

COMPOUNDS
Coordination compounds
A metal complex, also known as a coordination compounds, consists of a central metal atom
surrounded by ions and or molecules. The metal is generally a transition metal, lanthanide or
actinide. The ions or molecules that bind to the metal to form coordination compounds are called
ligands.
Coordination complex
A neutral or charged molecule that contains a central metal atom or ion surrounded by ligands.
Complex ion
A charged coordination complex that is stabilized by neighbouring counter ions.
1. Eg:- [Ni(NH)6)²⁺ is a complex ion in which the central ion Ni?* is surrounded by six ammonia
molecules.
2. Eg:- The complex ion [PtCl₂(NH₃)₄]²⁺ consist of the central platinum ion Pf2+
surrounded by 4 ammonium molecules and to chloride ion.
 The complex ion may positively charged. Eg:- [ Co(NH₃)₆]³⁺
 The complex ion may negatively charged. Eg :- [ Ag(CN)₂]
 The complexion is a neutral species. Eg:- [ CoCl₃(NH₃)₃] and [PICI₄(NH₃)₂]
complex
Liagand
 The ligand is a species that is capable of donating an electron pair to a Central
metal ion or atom. It is a Lewis base.
Type's of ligand
 1). Unidentate ligand: A ligand which contain only one atom which is capable of
donating an electron pair is known as Unidentate ligand. This is also known as
monodentate ligand. Eg:NH3,H20, CN-, Cl-, Br- etc.
 2). Bidentate ligand: A ligand which contain two atoms which are capable of
donating electron pairs is called a bidentate ligand. Eg: ethylenediamine, oxalate
ion.
 Coordination number: Coordination number of monodentate ligands directly
attached to the central metal ion through coordinate bonds.
 Coordination sphere: The central metal atom and ligands attached to it are
enclosed in square brackets and are collectively called coordination sphere. The
ligands and the central metal atom inside the square bracket behaves as single
WERNER’S THEORY OF
COORDINATION COMPOUNDS

Werner's theory, also known as the Werner complex theory, is a fundamental concept in coordination chemistry.
Alfred Werner proposed this theory in 1893 to explain the structure and properties of coordination compounds.
Postulates of Werner's Theory:-
 Metal ions possess two types of valences Primary valence (onizable) and secondary valence (non-
ionizable).
 Primary valence corresponds to the oxidation state Determined by the number of electrons lost or gained.
 Secondary valence corresponds to coordination number Number of ligands attached to the metal.
 Ligands are arranged around the metal in a specific geometry Determined by the coordination number.
 Ligands can be ionizable or non-ionizable lonizable ligands (e.g., CI-, NO3-) and non-ionizable ligands
(e.g., NH3, H2O).
 Complexes can be neutral, cationic, or anionic Depending on the charges of the metal and ligands.
 Isomerism exists in coordination compounds Structural, stereoisomerism, and linkage isomerism.
STRUCTURE OF COORDINATION COMPOUND
ON THE BASIS OF WERNER’S THEORY
VALENCE BOND THEORY

 1. The ligand → metal bond in a coordination complex is covalent in nature. It is formed by sharing of
electrons (provided by the ligands) between the central metal atom and the ligand.
 2. Each ligand should have at least one filled orbital containing a lone pair of electrons.
 3.In order to accommodate the electron pairs donated by the ligands, the central metal ion present in a
complex provides required number (coordination number) of vacant orbitals.
 4. These vacant orbitals of central metal atom undergo hybridisation, the process of mixing of atomic
orbitals of comparable energy to form equal number of new orbitals called hybridised orbitals with same
energy.
 5. The vacant hybridised orbitals of the central metal ion, linearly overlap with filled orbitals of the ligands
to form coordinate covalent sigma bonds between the metal and the ligand.
 6. The hybridised orbitals are directional and their orientation in space gives a definite geometry to the
complex ion.
 7 In the octahedral complexes, if the (n-I) d orbitals are involved in hybridisation, then they are called
inner orbital complexes or low spin complexes or spin paired complexes. If the nd orbitals are
involved in hybridisation, then such complexes are called outer orbital or high spin or spin free
complexes. Here n represents the principle quantum number of the outermost shell.
 8. The complexes containing a central metal atom with unpaired electron(s) are paramagnetic. If all
the electrons are paired, then the complexes will be diamagnetic.
 9.
Ligands such as CO, CN-, en, and NH3 present in the complexes cause pairing of electrons present
in the central metal atom. Such ligands are called strong field ligands.
 10. Greater the overlapping between the ligand orbitals and the hybridised metal orbital, greater is
the bond strength
CRYSTAL FIELD THEORY(CFT)

Crystal Field Theory (CFT), introduced in the early 20th century by Hans Bethe
and later developed by J. H. Van Vleck and Linus Pauling, revolutionized the
understanding of transition metal complexes. CFT focuses on the interaction
between the d-orbitals of the central metal ion and the ligand field generated
by surrounding ligands. Unlike earlier models, which treated metal-ligand
bonding as purely covalent or purely ionic, CFT provides a more nuanced
description incorporating both covalent and ionic contributions to the bonding.
The interaction between the d-orbitals of the central metal ion and the
electrons of surrounding ligands leads to the splitting of the degenerate d-
orbitals into different energy levels, forming a crystal field around the metal
center. The resulting energy difference between these levels gives rise to
various spectroscopic and magnetic properties observed in coordination
compounds
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 A. The opposite applies to the low spin complexes in which
strong field ligands cause maximum pairing of electrons in the set of three t, atomic
orbitals due to large Ao•
 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
 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-yand 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 "Ao"
(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.
The relative stabilizing effect of e set will be -6Dq and
the destabilizing effect of t2 set will be +4Dq
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 2g is
lowered by 4Dq and the eg level is raised by +6Dq.
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. 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. This is most commonly
observed with transition metal octahedral complexes, however, it can
be observed in tetrahedral compounds as well.
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 z ligand bonds 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: t2g daz, dys, day and eg d=2And da? -y?). 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 z ligand bonds
MOLECULAR ORBITAL THEORY

• The molecular orbital theory (often abbreviated to MOT) is a theory on chemical

bonding developed at the beginning of the twentieth century by F. Hund and R. S.
Mulliken to describe the structure and properties of different molecules. The valence-
bond theory failed to adequately explain how certain molecules contain two or more
equivalent bonds whose bond orders lie between that of a single bond and that of a
double bond, such as the bonds in resonance-stabilised molecules. This is where the
molecular orbital theory proved to be more powerful than the valence-bond theory
 The key features of the molecular orbital theory are listed below.
 The total number of molecular orbitals formed will always be equal to the total number
of atomic orbitals offered by the bonding species.
 There exist different types of molecular orbitals: bonding molecular orbitals, anti-
bonding molecular orbitals and non-bonding molecular orbitals. Of these, anti-bonding
molecular orbitals will always have higher energy than the parent orbitals, whereas
bonding molecular orbitals will always have lower energy than the parent orbitals.
 The electrons are filled into molecular orbitals in the increasing order of orbital energy
(from the orbital with the lowest energy to the orbital with the highest energy).
 The most effective combinations of atomic orbitals (for the formation of molecular
orbitals) occur when the combining atomic orbitals have similar energies.
The key features of the molecular orbital theory are listed below.
 The total number of molecular orbitals formed will always be equal to the total
number of atomic orbitals offered by the bonding species.
 There exist different types of molecular orbitals: bonding molecular orbitals, anti-
bonding molecular orbitals and non-bonding molecular orbitals. Of these, anti-
bonding molecular orbitals will always have higher energy than the parent orbitals,
whereas bonding molecular orbitals will always have lower energy than the parent
orbitals.
 The electrons are filled into molecular orbitals in the increasing order of orbital
energy (from the orbital with the lowest energy to the orbital with the highest
energy).
 The most effective combinations of atomic orbitals (for the formation of molecular
orbitals) occur when the combining atomic orbitals have similar energies.
COORDINATION NUMBER 7 COMPLEXES

 Coordination Number 7. Seven coordinate complexes are rare outside of the

relatively large early transition metals, lanthanides, and actinides. The three
common seven coordinate geometries are pentagonal bipyramidal, monocapped
octahedral, and monocapped trigonal prismatic.
 Coordination no :8
 The common geometries for a coordination number of 8 are: square
antiprismatic, dodecahedral, bicapped trigonal prismatic, cubic, and hexagonal
bipyramid.
 The cubic geometry is only found in ionic lattices, such as sCl, and in complexes
of inner transition metals, such as Na3[UF8].
 The body-centered cubic (BCC) structure is a metallic crystal structure with a
coordination number of 8. This means that each atom in the structure is
surrounded by 8
 other atoms
• Higher coordination compounds :
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