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Department of Chemistry University of Cape Town

Inorganic and Organic Chemistry CEM2008S Final Examination
Time : 2 hours

7th November, 2010

Marks: 85

INSTRUCTIONS TO CANDIDATES: 1. This paper consists of 2 sections: SECTION A: Organic Chemistry (Questions 1 6) SECTION B: Inorganic Chemistry (Questions 7 11) 2. Answer SECTION A in the spaces provided on this question paper. 3. Answer SECTION B in a separate answer book. 4. A periodic table is attached.

Question Mark

10

11

Total

SECTION A (47 Marks) Answer this section in the spaces provided on this question paper.

QUESTION 1 Consider the two reactions shown below. In the first reaction, the cyclopentane epoxide 1 is reacted with dimethylamine (Me2NH) to give two products, 2 and 3. In the second reaction, a substituted cyclopentane expoxide 4 is treated with the same reagent (Me2NH) and gives a single product 5.
OH O Me2NH NMe2 1 2 NMe2 O Me2NH OH NMe2

+
3

OH

(a)

Give mechanisms (using curly arrows) to explain the formation of the two products 2 and 3 in the first reaction. (2)

(b)

State the stereochemical relationship between 2 and 3. (1)

(c)

Give the mechanism for the formation of product 5 in the second reaction and explain why only one product is formed in this reaction. (2)

(d)

The epoxide 4 can be formed from alkene 6 shown below:

O ?

i.

4 Give the structure of the reagent or reagents required for this transformation and show the mechanism for the reaction. (2)

ii.

Give a reason why a single stereoisomer 4 is formed in this reaction (1)

(e)

With reference to the second reaction above (4 5), propose a sequence of reactions for transforming epoxide 7 below to the substituted cyclopentane 8. In each proposed step give the structures of the reagent and product, as shown for 4 5 above. (7)

several steps

N NH2

CH3 7 CH3 8

[15]

QUESTION 2 Consider the following two substitution reactions, both of which are considered to proceed via the SN1 mechanism:

PhS Na Reaction 1: Ph Br PhS Na Reaction 2: MeO Br MeO SPh + NaBr Ph SPh + NaBr

(a)

Explain, by discussing the mechanisms and proposed intermediates, why both reactions proceed via the SN1 mechanism, even though they both involve primary alkyl halides which are normally thought to favour the SN2 mechanism. (4)

(b)

How would the rate of Reaction 2 change if the concentration of both the alkyl halide and the nucleophile were doubled? (1)

[5]

QUESTION 3 Provide a detailed mechanism (using curly arrows) to explain the outcome of the reaction shown below: O Br 2 O OH O
Br

[3]

QUESTION 4 (a) Rank the following compounds according to increasing stability:

(2)

(b)

Complete the following table by predicting the most likely type of elimination (if any) that the compounds may undergo given reaction conditions below.

H2O, H+

EtOH, EtO-Na+

(2)

c)

(i) Draw two possible chair conformations (1 and 2) for compound A below, clearly indicating axial and equatorial substituents: 1: Most stable 2: Least stable

(3) (ii) An elimination takes place upon treatment of compound A with EtO-Na+ in EtOH. Provide a mechanism and the product for the reaction. (2)

[9]

QUESTION 5 Provide the major product(s) or reagents for the reactions listed below. All reagents are limiting unless stated otherwise.

(a)

(b)

(iii) (c)

(iv) (d)

(4x2) [8]

QUESTION 6 (a) Consider the reaction below where the directing effects of the substituents present in the reactant combine to give the product shown.

NHMe CH3Cl AlCl3 CN

NHMe CH3

CN
Major product

Explain the formation of the product by drawing all the possible resonance structures of the intermediates for this reaction. (5)

(b)

Propose a synthetic route from benzene to 3-bromobenzenesulfonic acid. Assume that you can separate ortho and para isomers if necessary. (2)

[7]

SECTION B (38 marks) Answer this section in the exam answer book provided. QUESTION 7 (a) The first four ionization energies for an element are (in MJ/mol): 0.899 1.757 14.848 21.006

How many valence electrons does this element have? Explain briefly. (2) (b) What is the trend in ionisation potentials as we go down a group in the Periodic Table (1) (c) Concisely explain what this trend in ionisation potentials is due to. (2) (d) Draw the structure of diborane(6) and describe the types of B-H bonds in the molecule. (2) (e) On the basis of VSEPR, predict the electron-pair geometry and molecular shape around the central atom in ICl2 . Draw the expected structure. Show any distortions from ideal geometries. (3)
-

[10]

QUESTION 8 (a) Using a Molecular Orbital Energy Diagram (MOED), explain why the OO bond length in O2 (1.26 ) is longer than that in the O2 molecule. Label each molecular orbital with its bond type, the atomic orbitals it was generated from, and whether it is bonding or antibonding. (6) (b) Sketch the lowest unoccupied molecular orbital (LUMO) of the superoxide anion, showing the phase of the different lobes. (2) [8]
-

QUESTION 9 (a) Correct each formula that has an error by providing the correct IUPAC formula for each of the following coordination compounds:

i. ii. iii.

potassium hexacyanocobaltate(III), K[Co(CN)6] hexaamminechromium(II), [Cr(NH3)5]2+ diamminetetrachloromanganate(II), [Mn(NH3)2Cl4]-1 (3)

(b)

Draw all possible stereoisomers for each of the following complexes.

Label the

diastereoisomers as cis or trans. If no stereoisomers are possible, indicate this fact and draw the only structure possible.

i. ii.

[Ni(NH3)2Cl2] (square planar) [Fe(en)2Br2]+ (en = ethylenediamine) (5) [8]

QUESTION 10 The coordination complex, [Cr(NH3)4Cl2)]Br, has been synthesized and isolated. Draw structures for all the possible inorganic isomers (e.g. linkage, hydration, optical, etc.). [4]

QUESTION 11 An octahedral transition metal complex [ML6]2+ (L is a neutral ligand) has a molar magnetic susceptibility (
m,

corrected for diamagnetism) of 1.09 x 10-2 cm3.mol-1 at 25 C.

(a) (b)

Calculate the number of unpaired electrons in the complex. Suggest identities for the M2+ first-row transition metal ion. Draw d-orbital splitting diagrams in support of your answers.

(c)

Which one of the possible transition metals (in b) is more likely to show a Jahn-Teller distortion? Explain your answer.

Useful equations: = 2.84(

mT) B

= {n(n+2)}

[8]