Chemistry 401

Intermediate Inorganic Chemistry

University of Rhode Island

Practice Problems

Exercises and Problems are from Shriver & Atkins, 4th edition. Some textbook examples have additional questions to the linked exercise or problem.


d-Metal Complexes

Exercise 8.3

Problem 19.4

Problem 8.6

Problem 20.1

Problem 8.7

Exercise 21.10

Problem 8.8

Exercise 19.5

1. (a) On a chart of the d-block elements in their periodic table arrangement, identify the elements and associated oxidation numbers that form square-planar complexes. (b) Give formulas for three examples of square-planar complexes. Answers

2. Sketch all the possible isomers of [Co(en)2(NO2)2], including optical isomers, in which the en ligands are bidentate. Do not draw different orientations of the same isomer. Answers

3. Give the name and find the ligand field stabilization energy (in terms of Dq) for the following complexes:

[Cr(NH3)6]3+

[Cu(NH3)4(OH2)2]2+

[Ti(OH2)6]3+

[Co(CN)6]3– (low spin)

[Ni(NH3)4Cl2]

Answers

4. Predict which of the following complexes is Jahn-Teller active:

[Cr(NH3)6]3+

[Cu(NH3)4(OH2)2]2+

[Ti(OH2)6]3+

[Co(CN)6]3–

[Ni(NH3)4Cl2]

Answers

5. Predict which of the following complexes will be stable:

[Mo(CO)6]

[(η6–C6H6)2Cr]

[(η3–C3H5)Co(CO)2]

[Fe(diphos)(CO)3] (diphos = Ph2PCH2CH2PPh2, Ph = C6H5)

Answers

6. Find the LFSE in terms of Dq and calculate the spin-only magnetic moment (in units of Bohr-magnetons) for the following complexes:

a) cis–diaqua–cis–dichloro–cis–difluorocobaltate(II) ion

b) trans–dicyanobis(ethylenediamine)iron(III) ion

c) trans–dichlorotetrakis(triphenylphosphine)nickel(II)

d) tris(bipyridine)ruthenium(II) ion

e) cis–dicyanobis(oxalato)manganate(II) ion

Answers

7. Predict whether the following complexes will be stable:

a) hexacarbonylvanadium(0)

b) bis(η5–cyclopentadienyl)bis(η1–cyclopentadienyl)titanium(IV)

c) bis(η4–cyclooctadiene)nickel(0)

d) hexacyanoferrate(III)

e) bis(η6–benzene)chromium(0)

Answers

8. Removing the all of the water from hydrates of transition metal complexes is notoriously difficult. Typically, simply heating the complex is ineffective and reaction with something like thionyl chloride is required. For example, cobalt(II) chloride hexahydrate only loses four water molecules to become cobalt(II) chloride dihydrate when heated in an oven at 150 °C. Suggest an explanation for this observation.

Answers

9. Find the LFSE (in terms of Dq and P) for: a) tris(oxalato)chromate(III) ion; b) hexacyanoferrate(II) ion; c) tetrachloro–η2–etheneplatinate(II) ion. Answers

10. Predict the stability of the following species: a) bis(η5–cyclopentadienyl)cobalt(II); b) tetracarbonylnickel(0); c) tricarbonyl(η5–cyclopentadienyl)manganese(I). Answers

11. Chromium (III) complexes are nearly all six-coordinate with octahedral geometry. Suggest a reason for this observation. Answers