Concept explainers
(a)
Interpretation:
For the given complex the orbital splitting diagram has to be drawn using spectrochemial series.
[Cr(H2O)6]3+
Concept introduction:
The element in the periodic table and count its position in the respective transition series. These elements are in Periods 5 and 6, so the general configuration is
[noble gas]ns2(n− 1)dx.
The spectrochemical series is
I−<Cl−<F−<OH−<H2O<SCN−<en<NO−2<CN−<CO
(a)
Explanation of Solution
Electron configuration of Cr: [Ar]4s13d5
Charge on Cr: The aqua ligands are neutral, so the charge on Cr is +3.
Electron configuration of Cr3+: [Ar]3d3
Six ligands indicate an octahedral arrangement. Using Hund’s rule, fill the lower energy
t2g orbitals first, filling empty orbitals before pairing electrons within an orbital.
(b)
Interpretation:
For the given complex the orbital splitting diagram has to be drawn using spectrochemial series.
[Cu(H2O)4]2+
Concept introduction:
The element in the periodic table and count its position in the respective transition series. These elements are in Periods 5 and 6, so the general configuration is
[noble gas]ns2(n− 1)dx.
The spectrochemical series is
I−<Cl−<F−<OH−<H2O<SCN−<en<NO−2<CN−<CO
(b)
Explanation of Solution
Electron configuration of Cu: [Ar]4s13d10
Charge on Cu: The aqua ligands are neutral, so Cu has a +2 charge.
Electron configuration of Cu2+: [Ar]3d9
Four ligands and a d9 configuration indicate a square planar geometry (only filled d sublevel ions exhibit tetrahedral geometry). Use Hund’s rule to fill in the nine d electrons. Thus, the correct orbital-energy splitting diagram shows one unpaired electron.
(c)
Interpretation:
For the given complex the orbital splitting diagram has to be drawn using spectrochemial series.
[FeF6]3−
Concept introduction:
The element in the periodic table and count its position in the respective transition series. These elements are in Periods 5 and 6, so the general configuration is
[noble gas]ns2(n− 1)dx.
The spectrochemical series is
I−<Cl−<F−<OH−<H2O<SCN−<en<NO−2<CN−<CO
(c)
Explanation of Solution
Electron configuration of Fe: [Ar]4s23d6
Charge on Fe: Each fluoride ligand has a –1 charge for a total charge of –6, so Fe has a +3 charge to make the overall complex charge equal to –3.
Electron configuration of Fe3+: [Ar]3d5
Six ligands indicate an octahedral arrangement. Use Hund’s rule to fill the orbitals.
F– is a weak-field ligand, so the splitting energy, Δ, is not large enough to overcome the resistance to electron pairing. The electrons remain unpaired, and the complex is called high-spin.
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Chapter 23 Solutions
Chemistry: The Molecular Nature of Matter and Change
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