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VBT theory
According to this theory, the structures of the complexes can be explained based on hybridization. The main assumption is that the metal-ligand bonds are formed by the donating of an electron pair by the ligand to the metal and thus form a coordinate bond between the metal and ligand. Strong field ligands: CN−, CO, en, NH3, NO2-, Py
[Co(CN)6]3- ion: In this complex, the oxidation state of cobalt is +3. The valence shell electronic configuration of Co3+ is 3d6. The CN– ligands are strong and therefore cause pairing of 3d-electrons. All six 3d-electrons are therefore paired and occupy three of the five 3d orbitals. The vacant 3d- orbitals combine with the vacant 4s and 4p orbitals to form six d2sp3-hybrid orbitals. These six hybrid orbitals overlap with six filled orbitals of ligands to form six-coordinate covalent bonds. [Fe(F)6]3- ion: In this complex, the oxidation state of Iron(Fe) is +3. The valence shell electronic configuration of Fe3+ is 3d5. The F- ligands are weak and therefore cause no pairing of 3d-electrons. All five 3d-electrons are therefore occupied on five 3d orbitals. The vacant 4s- orbitals combine with the vacant 4p and two vacant 5d orbitals mixed with each other to form six sp3d2-hybrid orbitals. These six hybrid orbitals overlap with six filled orbitals of ligands to form six-coordinate covalent bonds.
[NiCl4]2- ion: In this complex ion, the oxidation state of Ni is +2. The valence shell electronic configuration is 3d8. Since Cl– is a weak ligand, therefore no pairing of electrons will occur in 3d-orbitals. None of the five 3d- orbitals is vacant. Vacant 4s and 4p orbitals combine to give four sp3 hybrid orbitals. These four hybrid orbitals form bonds with four ligands by sharing four pairs of electrons.
[Ni(CN)4]2- ion: In this complex ion, the oxidation state of Ni is +2. The valence shell electronic configuration is 3d8. Since CN– is a strong ligand, therefore these ligands cause to pair up the two unpaired electrons in one d-orbital resulting in a vacant 3d-orbital. This vacant 3d-orbital gets hybridised with the vacant 4s and two 4p orbitals to give four dsp2 hybrid orbitals. These four hybrid orbitals form bonds with four ligands by sharing four pairs of electrons.
Limitations of Valence Bond Theory
It could not explain the nature of ligands.
It could not explain why the pairing of electrons occurs in the presence of strong ligands. It could not explain the colour and electronic spectra of complexes. It could not explain reaction rates and the mechanism of reactions of complexes. This theory does not provide any quantitative interpretation data about the thermodynamic and kinetic stability of coordination complexes.
Q. Is NiCl 4 2- ? paramagnetic or diamagnetic? In this complex, the oxidation state of Ni is +2. Since Cl- is a weak ligand, therefore no pairing of electrons will occur in 3d-orbitals. The valence shell electronic configuration is 3d8. There are 2 unpaired electrons present in the NiCl4 2- complexes. So this complex is paramagnetic in nature.
Q. What is the hybridization of NiCl 2-? 4
The hybridization of NiCl4 is sp3 hybridization. It shows tetrahedral geometry.
