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Course Unit Examination

28 April 2014

10:00 - 12.30

CHE312 Transition Metal Chemistry (Resit Examination)


Duration: 2 h 30 minutes

YOU ARE NOT PERMITTED TO START READING THIS QUESTION PAPER UNTIL INSTRUCTED TO
DO SO BY AN INVIGILATOR.

Answer Question 1, ONE Question from Section A and ONE Question from Section B.
A Periodic Table is provided. A marking scheme is provided for your guidance.

CALCULATORS ARE PERMITTED IN THIS EXAMINATION. PLEASE STATE ON YOUR ANSWER


BOOK THE NAME AND TYPE OF MACHINE USED.
COMPLETE ALL ROUGH WORKINGS IN THE ANSWER BOOK AND CROSS THROUGH ANY WORK
WHICH IS NOT TO BE ASSESSED.
IMPORTANT NOTE: THE ACADEMIC REGULATIONS STATE THAT POSSESSION OF
UNAUTHORISED MATERIAL AT ANY TIME WHEN A STUDENT IS UNDER EXAMINATION
CONDITIONS IS AN ASSESSMENT OFFENCE AND CAN LEAD TO EXPULSION FROM THE
COLLEGE. PLEASE CHECK NOW TO ENSURE YOU DO NOT HAVE ANY NOTES IN YOUR
POSSESSION. IF YOU HAVE ANY THEN PLEASE RAISE YOUR HAND AND GIVE THEM TO AN
INVIGILATOR IMMEDIATELY.
PLEASE BE AWARE THAT IF YOU ARE FOUND TO HAVE HIDDEN UNAUTHORISED MATERIAL
ELSEWHERE, INCLUDING TOILETS AND CLOAKROOMS IT WILL BE TREATED AS BEING FOUND IN
YOUR POSSESSION. UNAUTHORISED MATERIAL FOUND ON YOUR MOBILE PHONE OR OTHER
ELECTRONIC DEVICE WILL BE CONSIDERED THE SAME AS BEING IN POSSESSION OF PAPER
NOTES. MOBILE PHONES CAUSING A DISRUPTION IS ALSO AN ASSESSMENT OFFENCE.

EXAM PAPERS CANNOT BE REMOVED FROM THE EXAM ROOM.

Examiners: Prof A Vlcek and Prof A C Sullivan

Queen Mary, University of London, 2014

Page 2 of 6

1.

CHE312 (2014)

Answer all parts.


(a) Give the empirical formula of the compound in the unit cell below. What general structural
type does this unit cell represent? Name one other metal oxide which adopts this structural
type and comment briefly on its structure related properties.
[5 marks]

(b) Describe with the aid of annotated diagrams the major differences between the magnetic
properties exhibited by NiO and CrO2.
[5 marks]
(c) Explain what the lanthanide contraction refers to and give details of one important
consequence of this contraction for the d-block elements.
[5 marks]
(d) How and why does the occurrence of metalmetal bonding in complexes vary from the 3d
to the 4d and 5d series? Illustrate your answer with reference to complex anions [M2Cl9]3
of chromium, molybdenum and tungsten.
[5 marks]
(e) Sort the ligands listed below into the following three classes (i) pure -donors, (ii) - and
- donors, and (iii) -donors and -acceptors.
CO, H, NO+, Cl, CH3, NH3, NCS, H2O, CH3CN, 2,2'-bipyridine, NCS, P(OMe)3,
1,2-ethylenediamine
[5 marks]
(f) Complete the following equations for redox reactions and decide with reasoning whether
they are inner sphere or outer sphere or substitution reactions. Propose the intermediate
structure for any inner-sphere reactions (bpy = 2,2'-bipyridine).
(i) [Co(NH3)5Cl]2+ + [Cr(H2O)6]2+ + 5H2O
(ii) [Fe(CN)6]3 + [Co(CN)5]3
(iii) [Os(bpy)3]2+ + [Mo(CN)8]3
(iv) [Co(NH3)5Cl]2+ + H2O
[5 marks]

Question 1 continued overleaf

Page 3 of 6
CHE312 (2014)
(g) Determine the metal oxidation state and d-electron configuration in the following
complexes:
(i) Mo(CO)4(P(C6H5)3)2
(ii) [Cr(NH3)5F]2+
(iii) TiCl4
(iv) [CoCl4]2
(v) [Cu(2,2-bipyridine)2]+

[5 marks]

(h) Decide, with reasoning, which of the following complexes will undergo a large Jahn-Teller
distortion in its electronic ground state:
(i) [Cr(NH3)6]2+
(ii) [Cu(H2O)6]2+
(iii) [Cu(NH3)6]+
(iv) [Cr(H2O)6]3+
(v) [Ti(H2O)6]3+

[5 marks]

SECTION A
2.

Answer all parts.


(a) Spinels are technologically important oxides of the general formula AIIBIII2O4 in which one
metal ion occupies an octahedral site and the other occupies a tetrahedral site. Using
crystal-field theory, decide with reasoning which metal ion occupies the tetrahedral and
which the octahedral site in the following spinels:
(i) MnIIMnIII2O4
(ii) NiIIGaIII2O4
[10 marks]
(b) Volume of activation and entropy of activation are the two criteria commonly used to
elucidate the mechanism of a substitution reaction. Briefly discuss how these parameters
can distinguish between dissociative substitution and associative substitution mechanisms.
How are these parameters determined experimentally?
[10 marks]
(c) Using the complex [Fe(phen)2(NCS)2] as an example, explain the spin crossover effect.
How is it possible to induce the spin change and what are the possible applications of this
effect?
[10 marks]

Page 4 of 6

3.

CHE312 (2014)

Answer all parts.


(a) Using the values of the volume of activation given in the table below, state the prevalent
mechanism of the water-exchange reaction for each metal ion listed. Explain the
occurrence of a dissociative, associative and interchange mechanisms in terms of the metal
ion d-electron configuration.
[M(H2O)6]n+ + H2O* [M(H2O)5(H2O*)]n+ + H2O

M
V/cm3mol1

V2+
4.1

Mn2+
5.4

Fe2+
+3.7

Co2+
+6.1

Ni2+
+7.2

Ti3+
12.1

V3+
8.9

Cr3+
9.6

Fe3+
5.4
[10 marks]

(b) Arrange at least six typical ligands of your own choice into a spectrochemical series and
explain the increase in the ligand-field strength using MO arguments.
[10 marks]
(c) Considering the trans-effect, propose a synthetic strategy for the following two complexes,
in each case starting from [PtCl4]2:
cis-[PtCl2(NO2)(NH3)]
trans-[PtCl2(NO2)(NH3)]
[10 marks]
SECTION B
4.

Answer all parts.


(a) For each of the following equations give the general name for the type of reaction
illustrated and the oxidation states of the metals in the starting materials and products.
[10 marks]
(i) TiCl4 + 2KCl K2TiCl6
(ii) [Fe(H2O)6]2+ + H2O [Fe(H2O)5(OH)]+ + H3O+
(iii) [PtCl4]2 + NH3 [PtCl3(NH3)] + Cl
(iv) Rh(PPh3)2(CO)Cl + CH3I RhCH3(CO)Cl(PPh3)2I
(v) [Fe(CN)6]3 + [Co(edta)]2 [Fe(CN)6]4 + [Co(edta)]
(b) Give balanced equations for the following chemical reactions:
(i) hydrolysis of [Fe(H2O)6]3+
(ii) air oxidation of [Fe(H2O)6]2+
(iii) ethanol reduction of H2CrO4
[6 marks]
Question 4 continued overleaf

Page 5 of 6
CHE312 (2014)
(c) Provide a schematic representation of the co-enzyme Vitamin B12. Give schematic
representations to indicate the various ways in which the co-enzyme could potentially
transfer a methyl group.
[7 marks]
(d) Provide schematic diagrams of deoxy and oxyhaemoglobin units. Describe the effect on
the deoxy haemoglobin structure of dioxygen binding at one of the haem sites and the
nature of the bonding.
[7 marks]
5.

Answer all parts.


(a) Deduce the lowest energy form of 2S+1LJ for the ions Ti3+, Cu2+, Co2+ and Mn2+. [8 marks]
(b) Use crystal field splitting diagrams to assist in assigning ground term symbols of the type
2S+1
A, 2S+1T or 2S+1E to the complex ions:
[8 marks]
[Ti(H2O)6]3+, [Cu(H2O)6]2+, [Co(H2O)6]2+, [Mn(H2O)6]2+.
(c) Give appropriate spectroscopic Term labels for the lines 1 to 4 and points 5 and 6 marked
on the portion of the Tanabe-Sugano diagram, for octahedral d 3 ions given below. Define
the parameters E/B and /B on the diagram axes.
4

E/B

/B

[8 marks]
(d) For each of the following complex ions, state whether you would expect its magnetic
moment to have contributions from orbital angular momentum and/or spinorbit coupling.
(i) [Ti(H2O)6]3+
(ii) [Cu(H2O)6]2+
(iii) [Mn(H2O)6]2+
[6 marks]
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End of Paper