Coordinate Compounds

A coordination compound is a chemical species consisting of a central metal atom or ion that is
bonded to a group of molecules or ions called ligands. These ligands donate electron pairs to the
metal center to form coordinate covalent bonds (also called dative bonds).

They are called coordination compounds because the central metal coordinates (i.e., bonds) with
ligands through coordinate covalent bonds. In these bonds, the ligand acts as a Lewis base (electron
pair donor) and the metal ion acts as a Lewis acid (electron pair acceptor).

Key Characteristics of Coordination Compounds

1. Central metal atom/ion usually a transition metal.

2. Ligands can be neutral or charged.

3. Coordinate bonds are formed by lone pair donation from ligands.

4. Geometry is defined by coordination no. (4 for tetrahedral or square planar, 6 for octahedral)

5. They often exhibit isomerism (geometrical, optical, linkage).

General Rules of Naming Coordinate Compounds

1. Name the ligands first, then the metal.

o Ligands are named in alphabetical order irrespective of their charge.

o Prefixes such as di-, tri-, tetra-, etc., indicate the number of ligands.
Primary Valence and Secondary Valence in Coordination Compounds

Coordination compounds are described by two types of valences, based on how the metal forms
bonds with other species. These are:

1. Primary Valence (Oxidation State)

• The primary valence refers to the oxidation state of the central metal ion.

• It corresponds to the ionic bonds between the metal and counter ions outside the
coordination sphere.

• It is satisfied by ionic interactions and shows how much positive charge the metal possesses.

Example: [Fe(CN)6]3−

The oxidation state of iron (Fe) is +3, so the primary valence is 3.

2. Secondary Valence (Coordination Number)

• The secondary valence is also called the coordination number.

• It refers to the total number of coordinate bonds formed between the metal and ligands
within the coordination sphere.

• These bonds are coordinate covalent bonds, where the ligand donates a pair of electrons to
the metal.

Example: [Fe(CN)6]3−

• Six cyanide ligands are bonded to iron, so the secondary valence is 6.

• Primary valence tells us how much the metal ion is charged and how it balances with
counter ions.
• Secondary valence describes the geometry, structure, and bonding within the
complex.
• Both together define the chemical behavior and properties of coordination
compounds.
Types of Ligands Based on Denticity

Denticity refers to the number of donor atoms in a ligand that coordinate (attach) to the central
metal atom or ion. Based on this, ligands are classified as unidentate, bidentate, or polydentate.

1. Unidentate (Monodentate) Ligands

• These ligands have only one donor atom through which they coordinate to the metal.

• They form one coordinate bond with the metal ion.

2. Bidentate (Didentate) Ligands

• These ligands have two donor atoms that coordinate to the metal.

• They form two coordinate bonds, usually forming a ring structure with the metal (chelate).

3. Polydentate Ligands

• These ligands have more than two donor atoms and can coordinate through multiple sites.

• They form multiple bonds and often create stable chelate complexes.
Why Denticity Matters

• The number of bonds between ligand and metal affects the stability and geometry of the
complex.

• Polydentate ligands often lead to chelate effects, making complexes more resistant to
decomposition.

• Biological systems use polydentate ligands (like porphyrins in hemoglobin) for important
functions.

Chelate Ligands

A chelate ligand is a ligand that can form two or more coordinate bonds with a central metal ion
through different donor atoms in the same molecule. This forms a ring structure called a chelate
ring, which includes the metal ion and parts of the ligand.

Key Features of Chelate Ligands

1. Multidentate:

o Chelate ligands are multidentate, meaning they have two or more atoms with lone
pairs that can bind to the metal.

o The number of donor atoms attached to the metal is called the denticity of the
ligand.

2. Ring Formation:

o The ligand wraps around the metal, forming a stable ring structure.

o The metal is incorporated into the ring, leading to strong bonding.

 3. Greater Stability:

o Complexes with chelate ligands are more stable than those with similar
monodentate ligands. This is known as the chelate effect.

Examples of Chelate Ligands

The Chelate Effect

• Chelating ligands form multiple bonds at once, reducing the chances of ligand dissociation.

• This makes the complex more thermodynamically stable.

• It also increases the entropy when the ligand binds, contributing to the overall stability.

Magnetic Behaviour

➤ What causes magnetism in coordination compounds?

Magnetism arises from the presence of unpaired electrons in the metal’s d-orbitals. The more
unpaired electrons, the stronger the magnetic behaviour.
Hybridisation in Coordination Compounds

➤ What is hybridisation?

Hybridisation involves mixing of atomic orbitals to form new hybrid orbitals that participate in
bonding with ligands.

➤ How is hybridisation determined?

It depends on:

• The geometry of the complex,

• The oxidation state and electronic configuration of the metal,

• The number of ligands attached (i.e., coordination number).

Weak Field Ligands and Strong Field Ligands

The concept of weak field and strong field ligands comes from Crystal Field Theory (CFT), which
explains how ligands affect the energy levels of the metal's d-orbitals when they approach and form
bonds.

1. What are Weak Field Ligands?

• Weak field ligands produce a small crystal field splitting energy (Δ).

• They do not strongly disturb the metal’s d-orbitals.

• As a result, the pairing of electrons is not favored, and electrons tend to occupy higher
energy orbitals rather than pairing up.

• This leads to high-spin complexes — with many unpaired electrons.

2. What are Strong Field Ligands?

• Strong field ligands produce a large crystal field splitting energy (Δ).

• They strongly interact with the metal ion’s d-orbitals and cause significant splitting.

• They favor electron pairing in lower energy orbitals.

• This leads to low-spin complexes — with fewer unpaired electrons or none at all.
Summary
 • Magnetic behaviour depends on the number of unpaired electrons, influenced by ligand
strength and geometry.

• Hybridisation describes how orbitals of the metal mix to bond with ligands, depending on
coordination number and shape.

• Complexes with strong field ligands tend to be low-spin and sometimes diamagnetic.

• Complexes with weak field ligands tend to be high-spin and paramagnetic.

• Hybridisation types like d2sp3, sp3, sp3 and dsp2 explain the shape and bonding of the
coordination compound.

Very Short Answer Type Questions

Short Answer Type Questions

Long Answer Type Questions

[Co(C2O4)3]3-
Delta Isomer (Right Handed Twist)

In the Δ isomer, the ligands twist in a clockwise manner around the metal center.

It resembles a right-handed spiral when looking from one end of the axis.

Lambda Isomer (Left Handed Twist)

In the Λ isomer, the ligands twist in an anti-clockwise manner.

It resembles a left-handed spiral when looking from one end.

✔ These two isomers are mirror images (enantiomers).

✔ They have identical physical properties except for how they interact with plane-polarized light —
one rotates it clockwise and the other rotates it counterclockwise.
✔ They also interact differently with other chiral molecules (important in biochemical processes).

[PtCl2(en)2]2+

Coordination: Pt(II), six donor atoms → octahedral.

Ligands: two en (ethylenediamine, bidentate each donating two N atoms → 4 donor sites) + two Cl⁻
(monodentate → 2 sites).

Geometric isomers: cis and trans for the two Cl ligands.

• trans isomer is achiral (no optical isomers).

• cis isomer can be chiral — it exists as a pair of enantiomers (non-superimposable mirror

images), usually designated Λ (lambda) and Δ (delta) depending on the handedness (helicity)
of the chelate wrap.

Think of an octahedron with the Pt at the center and six vertices. Label three mutually perpendicular
axes x, y, z. Place the two chloride ligands cis (i.e. adjacent, 90° apart) — for convenience put them
on two adjacent vertices on the equatorial plane. The two en ligands each occupy two adjacent
coordination sites and form two five-membered chelate rings that wrap around the metal — the
direction of that wrap (right-handed or left-handed) gives Δ or Λ.

(A) Δ (Delta) isomer — right-handed twist

Interpretation:

• Two chloride ligands are adjacent (cis).

• The chelate rings (shown by the N—C—C—N sequences) wrap clockwise/right-handed

when viewed down a three-fold axis → Δ.

(B) Λ (Lambda) isomer — left-handed twist

Interpretation:

• Same cis arrangement of Cl ligands, but the two en chelates wrap counterclockwise/left-
handed → Λ.

Properties

• Cis-[PtCl₂(en)₂]²⁺ exists as a pair of enantiomers: Λ-cis and Δ-cis.

• They rotate plane-polarized light in opposite directions and have identical physical properties
except optical rotation and interactions with other chiral species.

• Trans-[PtCl₂(en)₂]²⁺ is centrosymmetric/achiral → no optical isomerism.

• IUPAC name (geometric): cis-dichloro-bis(ethylenediamine)platinum(II). Enantiomers are

named Λ-cis- and Δ-cis

[Cr(NH₃)₂Cl₂(en)]⁺
Here are the 3D representations of the optical isomers (Δ and Λ forms) of [Cr(NH₃)₂Cl₂(en)]⁺.

• The central Cr atom is in purple at the center.

• NH₃ ligands are in blue.

• Cl⁻ ligands are in green.

• The en (ethylenediamine) ligands are shown by red points indicating their nitrogen donor
atoms wrapping around the metal center.

✔ The Δ-isomer shows a right-handed twist.

✔ The Λ-isomer shows a left-handed twist.