UNIVERSITY OF LONDON

BSc/MSci DEGREE – June 2003, for Internal Students of Imperial

College London

This paper is also taken for the relevant examination for the
Associateship

Inorganic Chemistry 1

Monday 16th June, 2003, 9.30 – 11.30 pm

ANSWER ALL QUESTIONS

USE A SEPARATE ANSWER BOOK FOR EACH QUESTION.

WRITE YOUR EXAMINATION NUMBER ON EACH ANSWER
BOOK.

Y1INORGJune2003 Turn over

Q1 Inorganic Characterisation

Answer part (a) AND THREE of parts (b) to (f).

(a) Answer ALL parts.

F3C
P CF3
F3C

(i) Sketch and label the 19F and 31P nmr spectra of the molecule
above.
(6 marks)

(ii) Consider the related compound (CF3)2P(CCl3). Sketch the mass

spectrum of the molecular ion, indicating the relative intensities
of the peaks for the different isotopic combinations.
(4 marks)

(b) Draw and label all of the vibrational modes of the linear cation NO2+
and the non-linear radical species NO2•. Indicate which vibrational
modes in each compound are IR active.

(5 marks)

(c) Predict the likely nuclear spins (zero, integral or half integral) of the
following atoms: 6Li, 10B, 15N, 29Si, 32S, 39K. Explain your reasoning.

(5 marks)

(d) Explain the observation that [CoCl4]2- is bright blue whilst

[Co(OH2)6]2+ is pale pink.

(5 marks)

(e) With reference to the bonding involved, comment on the stretching

frequencies of M-C (M = Sc to Zn) and C-O bonds in metal-carbonyl complexes.

(5 marks)
(f) Sketch the 19F NMR spectra of PF5 at low and high temperatures.
Explain any differences in the spectra.

(5 marks)

INFORMATION AVAILABLE FOR THIS QUESTION:

Assume 12C: I = 0, abundance = 100 %; 14N: I = 0, abundance = 100 %;
19
F: I = ½, abundance = 100 %; 31P: I = ½, abundance = 100 %; 35Cl: I =
0, abundance = 75.5 %; 37Cl: I = 0, abundance = 24.5 %.
 Q2 Periodicity and Inorganic Reactivity
Answer part (a) AND ANY TWO parts (b) – (d)

(a) Answer BOTH parts

The mean bond dissociation enthalpies (in kJ mol-1) of Group 15 single and
triple bonds are given below:

N-N P-P As-As Sb-Sb

167 209 180 142

N≡N P≡P As≡As Sb≡Sb

945 493 380 293

(i) Discuss and account for the variation in these bond energies.
(7 marks)

(ii) Describe the elemental forms of both nitrogen and phosphorus, and use
the data above to help explain any differences.
(6 marks)

(b) The tetrachlorides of Si, Ge, Sn and Pb all hydrolyse rapidly in the
presence of water. Write an equation for this reaction and explain why
carbon tetrachloride does not readily undergo such a reaction.
(6 marks)

(c) Predict the outcome, if any, of the following reactions fully explaining
your answers:

F3B·NMe3 + BCl3 →

Cl3B·NMe3 + BF3 →
(6 marks)

(d) BeCl2 is monomeric and linear in the vapour state, although in the solid
state it forms polymeric infinite chains containing tetrahedral Be atoms.
Draw the structure of BeCl2 in each of these states indicating the
hybridisation of the Be centres and the type of bonding present. Suggest
a reason why BeCl2 likes to forms these polymers in the solid state.

(6 marks)
Q3 Coordination Chemistry
Answer part (a) AND EITHER part (b) OR part (c).

(a) For the following compounds, give the oxidation state of the transition
metal, and the number of d electrons in the metal's valence shell.

(i) K[MnO4]
−
(ii) [V(CO)2(PPh3)4]
(iii) [Fe(OH2)6]3+
(iv) [Ni(en)3]2+
(8 marks)

Give systematic names for the following two compounds:

Cl Br
Cl PEt3 NH3
H3N

Pt Co
H3N NH3
Cl PEt3
Cl

(4 marks)

(b) Answer BOTH parts of this question

Draw all the possible geometrical isomers of the following two systems and
in each case, identify the situations in which optical isomers are possible (A,
L, X, Y, Z represent different unidentate ligands).

(i) a four coordinate complex [ML2XY]

(3 marks)

(ii) an octahedral complex [MA2LXYZ]

(10 marks)
(c) Answer BOTH parts of this question:

(i) Using crystal field theory, explain why [Mn(OH 2)6]2+ which has five
- −
unpaired electrons, reacts with CN to form [Mn(CN)6]4 which has one
-
unpaired electron, but with I it gives [MnI4]2- which has five unpaired
electrons.
(6 marks)

(ii) With regard to the selection rules for electronic transitions, explain
3+
why [Ti(OH )6] is a weakly-coloured (violet) material and the
2
spectrum involves two overlapping absorptions.

(7 marks)