Class 12 Chemistry Notes Chapter 9 - Coordination Compounds

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Coordination compounds are molecules that poses one or multiple metal centers that is bound to ligands (atoms, ions, or molecules that donate electrons to the metal). These complexes can be neutral or charged. When the complex is charged, it is stabilized by neighboring counter-ions.

Werner’s Theory of Coordination Compounds

Alfred Werner (1866-1919), a Swiss chemist was the first to formulate his ideas about the structures of coordination compounds. He prepared and characterised a large number of coordination compounds and studied their physical and chemical behaviour by simple experimental techniques.

Werner proposed the concept of a primary valence and a secondary valence for a metal ion. Binary compounds such as CrCl3, CoCl2 or PdCl2 have primary valence of 3, 2 and 2 respectively.

Werner in 1898, propounded his theory of coordination compounds. The main postulates are:

  1. In coordination compounds metals show two types of linkages (valences)-primary and secondary.
  2. The primary valences are normally ionisable and are satisfied by negative ions.
  3. The secondary valences are non-ionisable. These are satisfied by neutral molecules or negative ions. The secondary valence is equal to the coordination number and is fixed for a metal.
  4. The ions/groups bound by the secondary linkages to the metal have characteristic spatial arrangements corresponding to different coordination numbers.

Difference between a double salt and a complex

Both double salts as well as complexes are formed by the combination of two or more stable compounds in stoichiometric ratio. However, they differ in the fact that double salts such as carnallite, KCl.MgCl2.6H2O, Mohr’s salt, FeSO4.(NH4)2SO4.6H2O, potash alum, KAl(SO4)2.12H2O, etc. dissociate into simple ions completely when dissolved in water. However, complex ions such as [Fe(CN)6] 4– of K4 [Fe(CN)6] do not dissociate into Fe2+ and CN– ions.

Definitions of Some Important Terms Pertaining to Coordination Compounds

(a) Coordination entity: A coordination entity constitutes a central metal atom or ion bonded to a fixed number of ions or molecules. For example, [CoCl3(NH3)3] is a coordination entity in which the cobalt ion is surrounded by three ammonia molecules and three chloride ions. Other examples are [Ni(CO)4], [PtCl2(NH3)2], [Fe(CN)6]4–, [Co(NH3)6]3+.

(b) Central atom/ion: In a coordination entity, the atom/ion to which a fixed number of ions/groups are bound in a definite geometrical arrangement around it, is called the central atom or ion. For example, the central atom/ion in the coordination entities: [NiCl2(H2O)4], [CoCl(NH3)5]2+ and [Fe(CN)6] 3– are Ni2+, Co3+ and Fe3+, respectively. These central atoms/ions are also referred to as Lewis acids.

(c) Ligands: The ions or molecules bound to the central atom/ion in the coordination entity are called ligands. These may be simple ions such as Cl–, small molecules such as H2O or NH3, larger molecules such as H2NCH2CH2NH2 or N(CH2CH2NH2)3 or even macromolecules, such as proteins.

(d) Coordination number: The coordination number (CN) of a metal ion in a complex can be defined as the number of ligand donor atoms to which the metal is directly bonded. For example, in the complex ions, [PtCl6]2– and [Ni(NH3)4]2+, the coordination number of Pt and Ni are 6 and 4 respectively.

(e) Coordination sphere: The central atom/ion and the ligands attached to it are enclosed in square bracket and is collectively termed as the coordination sphere. The ionisable groups are written outside the bracket and are called counter ions. For example, in the complex K4[Fe(CN)6], the coordination sphere is [Fe(CN)6]4– and the counter ion is K+.

(f) Coordination polyhedron: The spatial arrangement of the ligand atoms which are directly, attached to the central atom/ion defines a coordination polyhedron about the central atom. The most common coordination polyhedra are octahedral, square planar and tetrahedral. For example, [Co(NH3)6] 3+ is octahedral, [Ni(CO)4] is tetrahedral and [PtCl4] 2– is square planar. Fig. 9.1 shows the shapes of different coordination polyhedra.

(g) Oxidation number of central atom: The oxidation number of the central atom in a complex is defined as the charge it would carry if all the ligands are removed along with the electron pairs that are shared with the central atom. The oxidation number is represented by a Roman numeral in parenthesis following the name of the coordination entity. For example, oxidation number of copper in [Cu(CN)4]3– is +1 and it is written as Cu(I).

(h) Homoleptic and heteroleptic complexes: Complexes in which a metal is bound to only one kind of donor groups, e.g., [Co(NH3)6]3+, are known as homoleptic. Complexes in which a metal is bound to more than one kind of donor groups, e.g., [Co(NH3)4Cl2]+, are known as heteroleptic.

Nomenclature of Coordination Compounds

Nomenclature is important in Coordination Chemistry because of the need to have an unambiguous method of describing formulas and writing systematic names, particularly when dealing with isomers. The formulas and names adopted for coordination entities are based on the recommendations of the International Union of Pure and Applied Chemistry (IUPAC).

Formulas of Mononuclear Coordination Entities

The formula of a compound is a shorthand tool used to provide basic information about the constitution of the compound in a concise and convenient manner. Mononuclear coordination entities contain a single central metal atom. The following rules are applied while writing the formulas:

(i) The central atom is listed first.

(ii) The ligands are then listed in alphabetical order. The placement of a ligand in the list does not depend on its charge.

(iii) Polydentate ligands are also listed alphabetically. In case of abbreviated ligand, the first letter of the abbreviation is used to determine the position of the ligand in the alphabetical order.

(iv) The formula for the entire coordination entity, whether charged or not, is enclosed in square brackets. When ligands are polyatomic, their formulas are enclosed in parentheses. Ligand abbreviations are also enclosed in parentheses.

(v) There should be no space between the ligands and the metal within a coordination sphere.

Naming of Mononuclear Coordination Compounds

The names of coordination compounds are derived by following the principles of additive nomenclature. Thus, the groups that surround the central atom must be identified in the name. They are listed as prefixes to the name of the central atom along with any appropriate multipliers.

The following rules are used when naming coordination compounds:

(i) The cation is named first in both positively and negatively charged coordination entities.

(ii) The ligands are named in an alphabetical order before the name of the central atom/ion. (This procedure is reversed from writing formula).

(iii) Names of the anionic ligands end in –o, those of neutral and cationic ligands are the same except aqua for H2O, ammine for NH3, carbonyl for CO and nitrosyl for NO. While writing the formula of coordination entity, these are enclosed in brackets ( ).

(iv) Prefixes mono, di, tri, etc., are used to indicate the number of the individual ligands in the coordination entity. When the names of the ligands include a numerical prefix, then the terms, bis, tris, tetrakis are used, the ligand to which they refer being placed in parentheses. For example, [NiCl2(PPh3)2] is named as dichloridobis(triphenylphosphine)nickel(II).

(v) Oxidation state of the metal in cation, anion or neutral coordination entity is indicated by Roman numeral in parenthesis.

Isomerism in Coordination Compounds

Isomers are two or more compounds that have the same chemical formula but a different arrangement of atoms. Because of the different arrangement of atoms, they differ in one or more physical or chemical properties. Two principal types of isomerism are known among coordination compounds. Each of which can be further subdivided.

(a) Stereoisomerism

  • Geometrical isomerism: This type of isomerism arises in heteroleptic complexes due to different possible geometric arrangements of the ligands.
  • Optical isomerism: Optical isomers are mirror images that cannot be superimposed on one another. These are called as enantiomers. The molecules or ions that cannot be superimposed are called chiral. The two forms are called dextro (d) and laevo (l) depending upon the direction they rotate the plane of polarised light in a polarimeter.

(b) Structural isomerism

  • Linkage isomerism: Linkage isomerism arises in a coordination compound containing ambidentate ligand.
  • Coordination isomerism: This type of isomerism arises from the interchange of ligands between cationic and anionic entities of different metal ions present in a complex.
  • Ionisation isomerism: This form of isomerism arises when the counter ion in a complex salt is itself a potential ligand and can displace a ligand which can then become the counter ion.
  • Solvate isomerism: This form of isomerism is known as ‘hydrate isomerism’ in case where water is involved as a solvent.

Bonding in Coordination Compounds

Valence Bond Theory: According to this theory, the metal atom or ion under the influence of ligands can use its (n-1)d, ns, np or ns, np, nd orbitals for hybridisation to yield a set of equivalent orbitals of definite geometry such as octahedral, tetrahedral, square planar and so on.

Magnetic Properties of Coordination Compounds: The magnetic moment of coordination compounds can be measured by the magnetic susceptibility experiments. The results can be used to obtain information about the number of unpaired electrons and hence structures adopted by metal complexes.

Limitations of Valence Bond Theory: While the VB theory, to a larger extent, explains the formation, structures and magnetic behaviour of coordination compounds, it suffers from the following shortcomings:

(i) It involves a number of assumptions.

(ii) It does not give quantitative interpretation of magnetic data.

(iii) It does not explain the colour exhibited by coordination compounds.

(iv) It does not give a quantitative interpretation of the thermodynamic or kinetic stabilities of coordination compounds.

(v) It does not make exact predictions regarding the tetrahedral and square planar structures of 4-coordinate complexes.

(vi) It does not distinguish between weak and strong ligands.

Crystal Field Theory: The crystal field theory (CFT) is an electrostatic model which considers the metal-ligand bond to be ionic arising purely from electrostatic interactions between the metal ion and the ligand. Ligands are treated as point charges in case of anions or point dipoles in case of neutral molecules.

  • Crystal field splitting in octahedral coordination entities: In an octahedral coordination entity with six ligands surrounding the metal atom/ion, there will be repulsion between the electrons in metal d orbitals and the electrons (or negative charges) of the ligands.
  • Crystal field splitting in tetrahedral coordination entities: In tetrahedral coordination entity formation, the d orbital splitting is inverted and is smaller as compared to the octahedral field splitting.

Colour in Coordination Compounds: In the previous Unit, we learnt that one of the most distinctive properties of transition metal complexes is their wide range of colours. This means that some of the visible spectrum is being removed from white light as it passes through the sample, so the light that emerges is no longer white. The colour of the complex is complementary to that which is absorbed.

Limitations of Crystal Field Theory: The crystal field model is successful in explaining the formation, structures, colour and magnetic properties of coordination compounds to a large extent. However, from the assumptions that the ligands are point charges, it follows that anionic ligands should exert the greatest splitting effect.

Bonding in Metal Carbonyls

The homoleptic carbonyls (compounds containing carbonyl ligands only) are formed by most of the transition metals. These carbonyls have simple, well defined structures. Tetracarbonylnickel(0) is tetrahedral, pentacarbonyliron(0) is trigonalbipyramidal while hexacarbonyl chromium(0) is octahedral.

Importance and Applications of Coordination Compounds

The coordination compounds are of great importance. These compounds are widely present in the mineral, plant and animal worlds and are known to play many important functions in the area of analytical chemistry, metallurgy, biological systems, industry and medicine. These are described below:

  • Coordination compounds find use in many qualitative and quantitative chemical analysis. The familiar colour reactions given by metal ions with a number of ligands (especially chelating ligands), as a result of formation of coordination entities, form the basis for their detection and estimation by classical and instrumental methods of analysis.
  • Hardness of water is estimated by simple titration with Na2EDTA. The Ca2+ and Mg2+ ions form stable complexes with EDTA. The selective estimation of these ions can be done due to difference in the stability constants of calcium and magnesium complexes.
  • Some important extraction processes of metals, like those of silver and gold, make use of complex formation. Gold, for example, combines with cyanide in the presence of oxygen and water to form the coordination entity [Au(CN)2]– in aqueous solution. Gold can be separated in metallic form from this solution by the addition of zinc (Unit 6).
  • Similarly, purification of metals can be achieved through formation and subsequent decomposition of their coordination compounds.
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