Principal Quantum Number of the Metal
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20-6-2019
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Principal Quantum Number of the Metal
For a series of complexes of metals from the same group in the periodic table with the same charge and the same ligands, the magnitude of Δo increases with increasing principal quantum number: Δo (3d) < Δo (4d) < Δo (5d). The data for hexaammine complexes of the trivalent group 9 metals illustrate this point:
[Co(NH3)6]3+: Δo = 22,900 cm−1
[Rh(NH3)6]3+: Δo = 34,100 cm−1
[Ir(NH3)6]3+: Δo = 40,000 cm−1
The increase in Δo with increasing principal quantum number is due to the larger radius of valence orbitals down a column. In addition, repulsive ligand–ligand interactions are most important for smaller metal ions. Relatively speaking, this results in shorter M–L distances and stronger d orbital–ligand interactions.
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