Module-1: Nomenclature of Coordination Compounds
Introduction
Coordination compounds, also known as coordination complexes, consist of a central metal
atom or ion bonded to a surrounding array of molecules or anions (called ligands). These
compounds are of great significance in various fields, including chemistry, biology, and
materials science.
IUPAC Nomenclature of Coordination Compounds
The International Union of Pure and Applied Chemistry (IUPAC) has established systematic
rules for naming coordination compounds. Here are some key points:
1. Cation before Anion: The name of the cation is written before the anion.
2. Ligands Named First: Ligands are named before the central metal atom/ion. Anionic
ligands end in '-o' (e.g., chloride becomes chlorido, sulfate becomes sulfato). Neutral
ligands are typically given their molecular name, with some exceptions like water
(aqua), ammonia (ammine), and carbon monoxide (carbonyl).
3. Prefixes for Number of Ligands: Use prefixes to denote the number of each type of
ligand: di- (2), tri- (3), tetra- (4), penta- (5), hexa- (6).
4. Metal Name: The name of the central metal atom/ion follows the ligands. If the
complex is an anion, the metal ends with the suffix '-ate'.
5. Oxidation State: The oxidation state of the central metal is indicated in Roman
numerals in parentheses.
Examples:
[Co(NH3)6]Cl3: Hexaamminecobalt(III) chloride
K3[Fe(CN)6]: Potassium hexacyanoferrate(III)
Isomerism in Coordination Compounds
Isomerism in coordination compounds can be broadly classified into two types: structural
isomerism and stereoisomerism.
1. Structural Isomerism:
o Ionization Isomerism: Compounds with the same composition but yield
different ions in solution. Example: [Co(NH3)5Br]SO4 and
[Co(NH3)5SO4]Br.
o Coordination Isomerism: Exchange of ligands between cationic and anionic
entities of different metal ions. Example: [Co(NH3)6][Cr(CN)6] and
[Cr(NH3)6][Co(CN)6].
o Linkage Isomerism: Ligands can coordinate to the metal through different
donor atoms. Example: [Co(NH3)5(NO2)]Cl2 (nitro) and
[Co(NH3)5(ONO)]Cl2 (nitrito).
2. Stereoisomerism:
o Geometrical Isomerism: Different spatial arrangements of ligands. Example:
cis-[Pt(NH3)2Cl2] and trans-[Pt(NH3)2Cl2].
o Optical Isomerism: Non-superimposable mirror images, known as
enantiomers. Example: [Co(en)3]3+ (where en is ethylenediamine).
Stereochemistry of Complexes with 4 and 6 Coordination Numbers
1. Tetrahedral Complexes (Coordination Number 4):
o Example: [NiCl4]2-
o Typically exhibit tetrahedral geometry.
o Geometrical isomerism is rare due to the symmetrical nature of the
tetrahedron.
2. Square Planar Complexes (Coordination Number 4):
o Example: [Pt(NH3)2Cl2]
o Exhibit square planar geometry.
o Geometrical isomerism can occur, such as cis and trans forms.
3. Octahedral Complexes (Coordination Number 6):
o Example: [Fe(CN)6]4-
o Typically exhibit octahedral geometry.
o Geometrical isomerism and optical isomerism can occur in octahedral
complexes.
Chelate Effect of Polynuclear Complexes
The chelate effect refers to the increased stability of coordination compounds that contain
chelating ligands (ligands that can form more than one bond to the central metal atom/ion).
This effect is due to the formation of ring structures, which reduces the entropy loss during
complex formation and increases the overall stability.
Labile and Inert Complexes
Labile Complexes: These complexes undergo rapid ligand substitution reactions.
Example: [Cu(NH3)4]2+
Inert Complexes: These complexes undergo slow ligand substitution reactions.
Example: [Co(NH3)6]3+
Self-Study: IUPAC Nomenclature of Coordination Compounds with
Examples
1. [Pt(NH3)4Cl2]Cl2: Tetraamminedichloroplatinum(IV) chloride
2. [Cr(en)3]Cl3: Tris(ethylenediamine)chromium(III) chloride
3. [Fe(CO)5]: Pentacarbonyliron(0)
Stereochemistry of Complexes with 4 and 6 Coordination Numbers
Tetrahedral and square planar geometries.
Octahedral geometries and the types of isomerism.
Chelate Effect of Polynuclear Complexes
Explanation of chelating ligands and their stability.
Examples of chelate complexes.
Labile and Inert Complexes
Characteristics and examples of labile and inert complexes.
Factors influencing ligand substitution rates.
Stereochemistry refers to the spatial arrangement of atoms in molecules and complexes. For
coordination complexes, stereochemistry is crucial in determining the properties and
reactivity of the complex. Let's discuss the stereochemistry of complexes with coordination
numbers 4 and 6.
Coordination Number 4
Complexes with a coordination number of 4 typically exhibit two common geometries:
tetrahedral and square planar.
1. Tetrahedral Geometry:
o Structure: Four ligands are symmetrically arranged around the central metal
atom, forming a shape like a pyramid with a triangular base.
o Examples: [Ni(CO)4][Ni(CO)_4][Ni(CO)4], [ZnCl4]2−[ZnCl_4]^{2-}[ZnCl4
]2−
o Stereochemistry: Tetrahedral complexes are often non-chiral if all ligands are
the same, but they can be chiral if the ligands are different.
2. Square Planar Geometry:
o Structure: Four ligands are positioned at the corners of a square around the
central metal atom, all lying in the same plane.
o Examples: [PtCl4]2−[PtCl_4]^{2-}[PtCl4]2−, [Ni(CN)4]2−[Ni(CN)_4]^{2-}
[Ni(CN)4]2−
o Stereochemistry: Square planar complexes can exhibit cis-trans isomerism,
where the arrangement of different ligands can create distinct isomers.
Coordination Number 6
Complexes with a coordination number of 6 most commonly exhibit octahedral geometry,
although other geometries like trigonal prismatic are also possible but less common.
1. Octahedral Geometry:
o Structure: Six ligands are symmetrically arranged around the central metal
atom, forming an eight-faced polyhedron.
o Examples: [Fe(CN)6]3−[Fe(CN)_6]3-[Fe(CN)6]3−, [Co(NH3)6]3+
[Co(NH_3)_6]^{3+}[Co(NH3)6]3+
o Stereochemistry:
Facial (fac) and Meridional (mer) Isomerism: For complexes of the
type [Ma3b3][Ma_3b_3][Ma3b3], fac isomers have three identical
ligands occupying adjacent positions at the corners of one face of the
octahedron, whereas mer isomers have three identical ligands
occupying positions around the meridian of the octahedron.
Cis-Trans Isomerism: For complexes of the type [Ma4b2][Ma_4b_2]
[Ma4b2], cis isomers have two identical ligands adjacent to each other,
while trans isomers have them opposite each other.
Chirality: Octahedral complexes can also be chiral if they contain
bidentate ligands forming chelate rings, creating optical isomers
(enantiomers).
Understanding the stereochemistry of coordination complexes is crucial for predicting their
chemical behavior, reactivity, and physical properties such as color, magnetism, and
biological activity.