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FOCUS 9 Online Cumulative Example

You are an inorganic chemist interested in the impact of various ligands on the properties
of transition metal complexes. To explore changes systematically, you have prepared a
series of octahedrally coordinated cobalt(III) complexes of the form [Co(NH3)5X]n1,
where X 5 Cl2, NH3, H2O, NO 22, and NO22. Aqueous solutions of each compound were
prepared and the wavelength of maximum absorbance, ␭max, is given below.
Complex ␭max /nm

[CoCl(NH3)5]21 530
[Co(NH3)6]31 475
[Co(NH3)5OH2]31 495
[Co(NH3)5ONO]21 485
[Co(NH3)5NO2]21 460

(a) Name the [Co(NH3)5NO2]21 ion. (b) Calculate the ligand field splitting energy for
[Co(NH3)5OH2]21. (c) Predict the color of an aqueous solution of [Co(NH3)5ONO]21. (d)
From the information provided, place the ligands (Cl2, NH3, H2O, NO 22, and NO22) in order
of increasing ligand field splitting. (e) Draw the crystal field splitting diagram for [Co(NH3)6]31
and indicate if the complex is high or low spin and if it is diamagnetic or paramagnetic.
(f) Which ions in this study may have a significant impact on the pH of an aqueous solution?
PLAN (a) Follow the procedures in Toolbox 9C.1 and refer to Table 9C.1 to name the
compound.
SOLVE
(a) From Toolbox 9C.1 and Table 9C.1,
2+
The NO22 ligand is bound through an N atom and so it is
nitro(kN). There are five NH3 ligands; therefore, the name of
[Co(NH3)5NO2]21 is
pentaamminenitro(kN)cobalt(III) ion

PLAN (b) The ligand field splitting, DO, is equal to the energy of the electronic transi-
tion, DO 5 hc/␭. To report the ligand field splitting as a molar energy, multiply by
Avogadro’s constant.
SOLVE
(b) From DO 5 NAhc/␭ and the wavelength of maximum absorbance

A N h c
644
447444
48 6444
4744
448 64444744448
23
242 kJ∙mol–1
6.022 3 10 mol 21
3 6.626 3 10 J?s 3 2.998 3 108 m?s21
234
¢O 5
4.95 3 10 27 m
144424443
␭
5 2.42 3 105 J?mol 21 5 242 kJ?mol 21 495 nm

PLAN (c) Use the color wheel in Fig. 9D.7 and wavelength of maximum absorbance to
predict the color of the solution.
SOLVE
(c) 485 nm light is blue and from Fig. 9D.7,

Because the perceived color is opposite the absorbed color in a

color wheel, the solution will appear orange.

485nm

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2 Focus 9 Online Cumulative Example

PLAN (d) Because DO ~ 1/␭, use the reported wavelengths to identify the order of ligand
strengths.
SOLVE

(d) Because DO ~ 1/␭, the complex with the longest wavelength NO2– NH3 NO2– H2O Cl–
absorbance has the smallest DO, and so ligand field splittings are
in the order
Cl 2 , H2O , NO22 , NH3 , NO22

400 500 600

Wavelength, ␭/nm

PLAN (e) Identify the number of d-electrons in a Co31 ion, classify the ligands as strong
or weak field from their positions in the spectrochemical series (Fig. 9D.6), and then
judge if the complex is high spin or low spin. If the complex has unpaired electrons it is
paramagnetic, otherwise it is diamagnetic.
SOLVE

(e) Identify the number of d-electrons. 7 8 9 10

31 6 Mn Fe Co Ni
The Co ion is a d ion. 3d74s2

Tc Ru Rh Pd

Classify the ligand strength. Strong

NH3 is a strong field ligand. NH3

Weak

For a strong-field ligand, predict a low-spin t2g6 configuration.

Low-spin [Co(NH3)6]31 has no unpaired electrons and so it is

diamagnetic.

PLAN (f ) Identify ligands that have acidic protons or are capable of accepting protons
(Topic 6D).
SOLVE

(f) Complexes with aqua ligands can

form conjugate hydroxido complexes 3+ 2+
of a by loss proton and thereby lower
the pH of the solution. –H +

3Co(NH3 ) 5OH2 4 31(aq) 1 H2O(l) Δ

3Co(NH3 ) 5OH 4 21(aq) 1 H3O 1(aq)

None of the complexes form basic aqueous solutions because the positive charge of the
complex repels any approaching proton.