The reasons behind this can be explained by ligand field theory. Some ligands always produce a small value of, while others always give a large splitting. Square planar and other complex geometries can also be described by CFT.
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The lower energy orbitals will be d z 2 and d x 2 - y 2, and the higher energy orbitals will be d xy, d xz and d yz - opposite to the octahedral case.įurthermore, since the ligand electrons in tetrahedral symmetry are not oriented directly towards the d -orbitals, the energy splitting will be lower than in the octahedral case. In a tetrahedral crystal field splitting, the d -orbitals again split into two groups, with an energy difference of tet. These labels are based on the theory of molecular symmetry: they are the names of irreducible representations of the octahedral point group, O h.(see the O h character table ) Typical orbital energy diagrams are given below in the section High-spin and low-spin. The three lower-energy orbitals are collectively referred to as t 2g, and the two higher-energy orbitals as e g. In octahedral symmetry the d -orbitals split into two sets with an energy difference, oct (the crystal-field splitting parameter, also commonly denoted by 10 Dq for ten times the differential of quanta 3 4 ) where the d xy, d xz and d yz orbitals will be lower in energy than the d z 2 and d x 2 - y 2, which will have higher energy, because the former group is farther from the ligands than the latter and therefore experiences less repulsion. The stronger the effect of the ligands then the greater the difference between the high and low energy d groups. Thus the d-electrons closer to the ligands will have a higher energy than those further away which results in the d -orbitals splitting in energy.Ī higher oxidation state leads to a larger splitting relative to the spherical field. The electrons in the d -orbitals and those in the ligand repel each other due to repulsion between like charges. The theory is developed by considering energy changes of the five degenerate d -orbitals upon being surrounded by an array of point charges consisting of the ligands.
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CFT successfully accounts for some magnetic properties, colors, hydration enthalpies, and spinel structures of transition metal complexes, but it does not attempt to describe bonding.ĬFT was subsequently combined with molecular orbital theory to form the more realistic and complex ligand field theory (LFT), which delivers insight into the process of chemical bonding in transition metal complexes.