Chem 324 Final Examination 2010 December 11, 2010 Page 1 of 8

Chemistry 324
Final Examination

Saturday, December 11, 2010

Instructor: Dave Berg

Answer all questions in the booklet provided; additional booklets are

available if necessary. There are 180 minutes and 150 marks so ration
your time accordingly. A periodic table and an Orgel correlation
diagram are included with this examination. There are 8 pages including
additional resource materials.

Question Total
1 12
2 12
3 14
4 8
5 10
6 12
7 14
8 12
9 14
10 14
11 14
12 14

Total 150
Chem 324 Final Examination 2010 December 11, 2010 Page 2 of 8

1. Draw the structures of the following complexes or complex ions. [12 pts]

(a) hexa(aquo)chromium(III) nitrate

(b) [Λ-cis-Co(acac)2(NH3)2]+
(c) trans-[Ni(CO)Cl]2(μ-Cl)2
(d) bis(κ2-(O,O)-acetato)copper(II)
(e) [(κ2-(S,O)-SO2)Pt(NH3)Cl]
(f) Mn(O)2(Cl)2 (O here is oxo)

2. Indicate whether each of the following statements is true or false and justify
your answer with a brief explanation. [12 pts]

(a) The pKa of H2O changes from about 14 in free water to between 22 and
24 when it is complexed in [Ti(OH2)6]3+.
(b) VSEPR is usually valid for d10 metal complexes.
(c) Square planar complexes can easily rearrange through a tetrahedral
intermediate at room temperature.
(d) Ligand rearrangement in 6-coordinate complexes often involves either
ligand loss or ligand gain.
(e) Berry pseudo-rotation is a ligand rearrangement that proceeds through a
trigonal prismatic intermediate.
(f) A dodecahedron is normally the least stable 8-coordinate structure and is
therefore very rarely observed.

3. Answer the following questions about isomerization in metal complexes.

(a) Draw the structures and indicate the isomer

stereochemistry (egs. cis, trans, mer, fac, etc.)
possible for all isomers of i) Co(dien)Cl3 and N

N terpy N

ii) Co(terpy)Cl3. [6 pts]

Chem 324 Final Examination 2010 December 11, 2010 Page 3 of 8

(b) Do any of the isomers in Q3(a) above exist as a pair of enantiomers

(that is, are any of these isomers chiral)? [2 pts]
(c) Draw a plausible example of a pair of hydration isomers. [3 pts]
(d) Draw a plausible example of a pair of ionization isomers. [3 pts]

4. Use a simple molecular orbital diagram to illustrate why ligands such as

CO or ethylene lead to larger ∆o in octahedral complexes compared to
simple σ-donors like NH3. Be sure to illustrate the specific orbital
interactions involved. [8 pts]

5. (a) Arrange the following ligands in order of increasing ∆o: bipy, CN-,
H2O, I-. [2 pts]
(b) Predict the magnetic susceptibility behaviour of the ferrocyanide
[Fe(CN)6]4- and [Fe(H2O)6]2+ ions. Give a reason for any difference.
[2 pts]
(c) Suggest a reason why all six Cr-O bonds in the structure of Cr(acac)3
are 1.96 Å while Mn(acac)3 shows four bonds at 1.91 Å and two at
2.09 Å. [3 pts]
(d) Explain why there are virtually no tetrahedral Pd2+ complexes while
Ni2+ can adopt either a square planar or tetrahedral geometry. [3 pts]

6. Answer the following questions about the electronic states of ions.

(a) Explain in words, what the Russell-Saunders terms represent. [3 pts]

(b) Determine the Russell-Saunders ground state term of an f6 ion. [3 pts]
(c) Determine the states arising when a 4D term is placed in a linear ligand
field. Assume the ligands lie along the z axis. [4 pts]
(d) What is the total degeneracy of a 5G term? [2 pts]
Chem 324 Final Examination 2010 December 11, 2010 Page 4 of 8

7. Answer the following questions about electronic spectroscopy.

(a) Explain why the Laporte symmetry rule is often relaxed (partially
violated) in real complexes. [3 pts]
(b) Explain why the molar absorptivity of [Co(H2O)6]2+ is 10 L mol-1 cm-1
while that for [CoCl4]2- is 600 L mol-1 cm-1. [2 pts]
(c) Predict how many absorption bands there will be (assuming no
overlap) in the UV/Vis spectrum of [Cr(NH3)6]2+. [3 pts]
(d) How does this change if two of the NH3 are replaced by Cl- in trans-
Cr(NH3)4(Cl)2 ? [3 pts]
(e) Explain why, in terms of electronic transitions, substituting two of the
NH3 in [Cr(NH3)6]2+ by bipy to form [Cr(NH3)4(bipy)]2+ leads to a
much more intensely coloured (ε>45,000 L mol-1 cm-1) complex. [3 pts]

8. Answer the following questions about magnetism.

(a) Define the magnetic moment, μ. [2 pts]

(b) Sketch Curie law behaviour for a simple paramagnet? [3 pts]
(c) Calculate the spin-only magnetic moment, μs, for high spin
[Co(H2O)6]2+. Is this value likely to agree with the observed moment?
Explain why or why not in detail. [4 pts]
(d) Briefly discuss the mechanism of antiferromagnetic coupling. [3 pts]

9. Zn2+ forms complexes with ligands L1 and L2 (next page) with the following
thermodynamic data:

L1 L2
log K 11.25 15.34
∆Ho (kJ mol-1) -44.4 -61.9
∆So (J mol-1 K-1) 66.5 85.8
Chem 324 Final Examination 2010 December 11, 2010 Page 5 of 8

L1 L2

NH HN NH HN

NH2 H 2N NH HN

(a) Write the mathematical equation for the formation constant K of Zn2+
(aq) with ligand L1 in water. [3 pts]
(b) Suggest reasons why the enthalpy AND entropy are BOTH more
favourable for complexation with L2. [4 pts]
(c) Would you expect complexation with L2 to be more or less favourable
(greater or smaller K value) with Ni2+ instead of Zn2+? Be sure to
consider all factors in arriving at your answer. [HINT: ion size is not a
factor here] [4 pts]
(d) Would you expect complexation with L1 to be more or less favourable
with Hg2+ instead of Zn2+? [3 pts]

10. (a) Comment on the large difference in water exchange rates between
Ru3+(aq) and Fe3+(aq) (a difference of about 108 in rate). Indicate which
is fast and which is slow as part of your answer. [4 pts]
(b) Predict which transition metal ions will have the fastest water
exchange rates of all, giving a rationale for your answer. [3 pts]
(c) The following rate data has been obtained for water substitution by the
ligand specified in [Ru(EDTA)(H2O)]-. Note this is an octahedral Ru3+
complex where one carboxylate arm of the EDTA is not bound to the
metal.

Ligand k (M-1 s-1) ∆H‡ (kJ mol-1) ∆S‡ (J mol-1 K-1)

pyridine 6300 7.0 -20
SCN- 270 8.9 -18
CH3CN 30 8.3 -24

(i) What does the data given suggest about the substitution
mechanism? [4 pts]
Chem 324 Final Examination 2010 December 11, 2010 Page 6 of 8

(ii) If the reverse reaction with water substituting CH3CN has a rate
constant k-1 = 300 M-1 s-1 what is the equilibrium constant Keq
for the following reaction? [3 pts]

k1
[Ru(EDTA)(H2O)]- + CH3CN [Ru(EDTA)(CH3CN)]- + H2O
k-1

11. [PtCl4]2- is a well known square planar anion.

(a) Give the most likely product for reaction of this anion with: [3 pts each]
(i) excess ethylene (C2H4)
(ii) excess I-
(iii) excess water
(b) Would the reaction with ethylene proceed faster if the ethylene pressure
was increased? Explain. [3 pts]
(c) Which 195Pt-31P coupling constant would be largest in [Pt(PPh3)3Cl]+?
Explain. [2 pts]

12. Answer the following questions about oxidative addition and reductive
elimination reactions.

(a) Complexes of the type Pt(PR3)4 form cis-PtCl2(PR3)2 when heated in

dilute aqueous HCl. Propose an explanation for this result using
chemical equations to illustrate your answer. [5 pts]
(b) Give the product formed when Vaska’s complex (trans-
IrCl(CO)(PPh3)2) reacts with H2 gas. [2 pts]
(c) What is the effect on the reaction in Q12(b) above when the phosphine
is changed from PPh3 to PF3? Explain. [3 pts]
(d) Explain how a ‘crossover’ experiment can be used to rule our
intermolecular reductive elimination by cis-Pd(CH3)2(PPh3)2. [4 pts]

[END: Orgel Diagram and Periodic Table Follow]

Chem 324 Final Examination 2010 December 11, 2010 Page 7 of 8

General Orgel correlation diagram for Oh and Td geometries

Chem 324 Final Examination 2010 December 11, 2010 Page 8 of 8