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Complex

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What is Complex?

A metal ion is at the centre of a complex ion, which is surrounded by a number of other molecules or ions. These can be thought of as co-ordinate (dative covalent) bonds linked to the central ion. (In some circumstances, though, the bonding is more intricate.)

As we already discussed what is complex, now we will discuss what is the meaning of complex in detail.


What is the Meaning of Complex?

A covalent bond is established when two atoms share a pair of electrons. Because both nuclei are attracted to the electron pair, the atoms are stuck together. Each atom contributes one electron to the formation of a simple covalent connection, although this isn't always the case.

A covalent link (a shared pair of electrons) in which both electrons come from the same place is known as a co-ordinate bond (also known as a dative covalent bond).

Example of a Complex Substance:


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Nomenclature in Complex Chemistry

Complex substances have their own naming convention: The central metal ion is the name given to the metal. Ligands are the anions or molecules that are bonded to the metal. The coordination number refers to the number of ligand-binding sites on the metal ion. A coordinate covalent bond is a link between a metal ion and a ligand in which the ligand gives both electrons. Water, ammonia, and chloride ions are examples of simple ligands.

Because coordination complexes are so common, their structures and reactions are explained in a variety of ways, which can be misleading. The donor atom is the atom in a ligand that is bound to the central metal atom or ion. A metal ion is bound to numerous donor atoms in a typical complex, which can be the same or different. A polydentate (many bonded) ligands is a molecule or ion having many bonds to the core atom; ligands with 2, 3, 4, or even 6 connections to the central atom are frequent. These complexes are known as chelate complexes, and the process of forming them is known as chelation, complexation, and coordination.


Ion in Complex Chemistry

All of these have active lone pairs of electrons in the outer energy level in common. The metal ion is employed to establish coordinate bonds with them.

Lone pair donors are present in all ligands. To put it another way, all ligands act as Lewis bases.

A complex substance is one in which one or more ligands are datively linked to a core metal cation. A ligand is a substance that can create a dative covalent connection with a transition metal by using its lone pair of electrons. H2O, NH3, Cl-, OH-, and CN- are examples of ligands.

Complex Ion-Forming Cations Must Have Two Characteristics:

  1. The presence of a high charge density attracts electrons from ligands.

  2. Low-energy empty orbitals that can accept the lone pair of electrons from ligands.

D-block metal (transition metal) cations are small, have a high charge, and have low-energy vacant 3d and 4s orbitals. When their partially full d subshell absorbs donated electron pairs from other ions or molecules, they readily form complex ions. The coordination number of a cation is the maximum number of lone pairs of electrons it can receive. This number is determined by the cation's size and electronic configuration, as well as the ligand's size and charge. The most common coordination number is six, but 4 and 2 are also popular. [Fe(H2O)6]2+, [CoCl4]2-, [Cu(NH3)4(H2O),2]2+, and [V(H2O)6]3+ are examples of complex ions.


Complex Ion Equilibria

When two reactants are combined, the reaction usually does not finish. Rather, until a condition is reached in which the concentrations of the reactants and products remain constant, the reaction will produce products. At this stage, the rate of product production is the same as the rate of reaction formation. Chemical equilibrium exists between the reactants and products, and it will continue to exist until it is disrupted by an external force. The reaction's equilibrium constant (Kc) links the concentrations of the reactants and products. The reaction between the iron (III) ion and the thiocyanate ion, for example, is as follows:

Fe3+(aq)+SCN-(aq)→FeSCN2+(aq)

The deep red thiocyanatoiron (III) ion ([ FeSCN]2+) is generated when Fe3+ and thiocyanate ion solutions are combined. The initial concentrations of Fe3+ and SCN will drop as a result of the reaction. One mole of Fe3+ and one mole of SCN will react for every mole of [ FeSCN]2+ produced. 


Complex Substance Equilibria

At a fixed temperature, the value of Kc remains constant. This indicates that Fe3+ and SCN mixes will react until the equation above is met. Regardless of the initial amounts of Fe3+ and SCN utilised, the Kc value will be the same. The appearance of the red colour — indicating the developing [FeSCN]2+ ion — can be measured using spectrophotometry to find Kc for this reaction experimentally. At 447 nm, the wavelength at which the red complex absorbs the maximum light, the amount of light absorbed by the complex is measured. The complex's absorbance (A) is proportional to its concentration (M) and can be directly measured using a spectrophotometer:

A = kM

The Beer-Lambert Law is a relationship between the amount of light absorbed and the concentration of the substance that absorbs the light, as well as the length of the path along which the light passes:

The observed absorbance (A) is proportional to the molar absorptivity constant (), route length (b), and molar concentration (c) of the absorbing species in this equation. The equation depicts the relationship between concentration and absorbance.

A = ϵbc

The coordination number refers to the total number of points of attachment to the centre element, which can range from 2 to 16 but is usually 6. In simple terms, the relative sizes of the metal ion and the ligands, as well as electronic parameters such as charge, which is reliant on the metal ion's electron configuration, determine the coordination number of a complex. The phrase ionic potential, which is defined as the charge to radius ratio (q/r), is used to explain these opposing effects.


Did You Know?

Electronic transitions caused by light absorption produce spectacular colours in transition metal complexes. As a result, they're frequently used as pigments. D–d transitions or charge transfer bands are the most common transitions associated with coloured metal complexes. D–d transitions occur only for partially-filled d-orbital complexes (d1–9) because an electron in a d orbital on the metal is excited by a photon to another d orbital of higher energy. Charge transfer is still possible in complexes with d0 or d10 configurations, even though d–d transitions are not. An electron is promoted from a metal-based orbital to an empty ligand-based orbital in a charge transfer band (metal-to-ligand charge transfer or MLCT). 

Excitation of an electron in a ligand-based orbital into an empty metal-based orbital also happens (ligand-to-metal charge transfer or LMCT). Electronic spectroscopy, also known as UV-Vis, can be used to observe these phenomena. Tanabe–Sugano diagrams can be used to assign d–d transitions to simple compounds with high symmetry. With the help of computation, these assignments are becoming more popular.

FAQs on Complex

1. What is a complex or coordination compound in chemistry?

A complex or coordination compound consists of a central metal atom or ion that is bonded to a group of surrounding molecules or ions, known as ligands. Unlike simple salts, these compounds retain their identity even when dissolved in water. For example, in K₄[Fe(CN)₆], the [Fe(CN)₆]⁴⁻ ion is the complex ion where Fe²⁺ is the central metal ion and CN⁻ are the ligands.

2. What is the main difference between a double salt and a complex compound?

The primary difference lies in their behaviour when dissolved in an aqueous solution.

  • A double salt, like Mohr's salt (FeSO₄·(NH₄)₂SO₄·6H₂O), dissociates completely into its constituent ions in water.
  • A complex compound, like potassium ferrocyanide (K₄[Fe(CN)₆]), does not dissociate completely. It yields a complex ion, [Fe(CN)₆]⁴⁻, which remains as a single stable entity in the solution, along with the counter ions.

3. What are ligands and how are they classified based on denticity?

A ligand is an ion or molecule that donates at least one pair of electrons to a central metal atom/ion to form a coordinate bond. They are classified based on the number of donor atoms they use to bind to the metal, a property called denticity. The main types are:

  • Monodentate: Ligands with one donor atom (e.g., H₂O, NH₃, Cl⁻).
  • Bidentate: Ligands with two donor atoms (e.g., ethylenediamine (en), oxalate ion (ox)).
  • Polydentate: Ligands with several donor atoms (e.g., EDTA, which is hexadentate).

4. Why are most transition metal complexes coloured?

The colour in transition metal complexes is primarily due to a phenomenon called d-d transition. In the presence of ligands, the d-orbitals of the central metal ion split into two different energy levels. An electron from a lower energy d-orbital can absorb light of a specific wavelength from the visible spectrum to jump to a higher energy d-orbital. The colour we perceive is the complementary colour of the light that was absorbed. For this to occur, the central metal ion must have a partially filled d-orbital.

5. How does the formation of a complex ion increase the solubility of a sparingly soluble salt?

The formation of a stable complex ion can significantly increase the solubility of a sparingly soluble salt by removing product ions from the dissolution equilibrium. For instance, silver chloride (AgCl) is not very soluble in water. However, upon adding ammonia (NH₃), the Ag⁺ ions react to form the highly stable and soluble complex ion [Ag(NH₃)₂]⁺. This consumption of Ag⁺ ions, as per Le Chatelier's principle, shifts the equilibrium AgCl(s) ⇌ Ag⁺(aq) + Cl⁻(aq) to the right, causing more solid AgCl to dissolve.

6. What is the importance of complex compounds in biological systems?

Complex compounds are absolutely vital for many biological processes. Key examples include:

  • Haemoglobin: The protein that carries oxygen in our blood is a complex of iron.
  • Chlorophyll: The pigment essential for photosynthesis in plants is a complex of magnesium.
  • Vitamin B12: A coenzyme critical for metabolism and the formation of red blood cells is a complex of cobalt.
These complexes perform highly specific functions that simple ions cannot.

7. How does Crystal Field Theory (CFT) explain why some complexes are high-spin while others are low-spin?

Crystal Field Theory explains this by comparing two key energies: the crystal field splitting energy (Δ), which is the energy difference between the split d-orbitals, and the pairing energy (P), which is the energy required to pair two electrons in the same orbital.

  • If Δ < P (common with weak-field ligands), it is energetically easier for electrons to occupy the higher energy orbitals than to pair up. This results in a high-spin complex with a maximum number of unpaired electrons.
  • If Δ > P (common with strong-field ligands), it is more favourable for electrons to overcome the pairing energy and fill the lower energy orbitals first. This leads to a low-spin complex with fewer unpaired electrons.