EXAMINATION MEMO NOVEMBER 2015

FACULTY OF SCIENCE AND AGRICULTURE

DEPARTMENT OF CHEMISTRY
SCHM312- Inorganic Chemistry
DURATION: 3 HOURS

MARKS: 100
SUBMINIMUM: 40%

Internal Examiner
Dr TV Segapelo
Prof N Revaprasadu
External Examiner
Prof MJ Moloto (VUT)

1.
2.
3.
4.

INSTRUCTION TO CANDIDATES
Please ascertain that this paper has six (6) pages.
Answer ALL FOUR (4) questions.
Number the questions correctly.
Write neatly.

Question 1

1.1

Answer the following questions on Titanium (Z= 22)

(a)

Give the electronic configuration of titanium.

2

(1)

1s 2s 2p 3s 3p 3d 4s
(b)

List its common oxidation states.

-1,0, +1,+2,+3
Page 1 of 13

(2)

(c)

Explain why titanium is difficult to extract.

(3)

It has a high melting point. Reacts readily with air, oxygen, nitrogen and
hydrogen at high temperatures. Forms carbides. Reduction with highly
electropositive metals like Na, Ca, or Mg cannot remove all the

oxygen

completely.
(d)

Give equations that describe the Van-de-Boer method of extraction.

(2)

Ti (impure) + 2I2 TiI4 Ti + 2I2

(e)

Give a balanced equation for the preparation of TiF4.

(1)

TiCl4 + HF TiF4 + HCl

(f)

Is bonding in TiF4 ionic or covalent?

(1)

Covalent
1.2

(a)

Give four oxides of vanadium and their respective colours.

(2)

V2O5 (yellow)

(b)

VO2 (deep blue)

V2O3 (green)
VO (grey black)
Give one pentahalide of vanadium.

(1)

VF5
1.3

Consider the following elements and answer the questions that follow:
W,Cr, Zr, Mn, Co, Fe, Ni
Which of the element/s,

1.4

(a)

does not form halides at high oxidation states. Mn

(b)

forms oxides which are acidic. Cr

(c)

does not react with H2 or N2. Co

(d)

forms alkoxides. Zr

(e)

is refractive , W

(15)

Complete the following reactions

(a)

V2O5 + NaOH Na3VO4 + H2O

(b)

Cr2O3 + Al Cr + Al2O3

(c)

MnO2 + H2SO4 MnSO4 + O2 + H2O

(d)

ZrCl4 + EtOH Zr(OEt)4 + 4HCl

Page 2 of 13

(e)
1.5

Cu + HNO3 Cu(NO3)2 + NO + H2O

(15)

Discuss two chemical properties of nickel.

(2)

Resistant to attack by air or water.

Ni has ability to absorb hydrogen when finely divided.
[25]

Question 2
2.1

Use the following complexes to illustrate the types of isomerism found in

transition metal complexes. Marks will only be allocated for a correct pair.
(a)

[Co(NH3)3(NO2)3]

NH3

NH3
NO2

H3N
Co

Co
NO2

H3N

ONO

H3N

NO2

ONO

Linkage isomerism

NH3

NH3
NO2

H3N

ONO

H3N

NO2

H3N

Co

Co
NO2

H3N

NH2

O2N

NO2

NO2

fac-isomer

mer-isomer

geometric isomerism

Page 3 of 13

(b)

[Co(NH3)4Cl2]NO2
NH3

NH3
Cl

H3N
Co

Co

NO2
Cl

H3N

NO2

H3N

NH3

ionization isomerism

NH3

NH3
Cl

Co

NH3

Cl
Co

NO2
Cl

H3N

NO2
Cl

H3N

NH3

NH3

cis-isomer

trans-isomer

geometric isomerism
2.2

Cl

H3N

NH3

H3N

Cl

(6)
Red crystalline [NiCl2(PPh2CH2Ph)2] is diamagnetic. On heating to 387 K for 2
hours, a blue-green form of the complex is obtained, which has a magnetic
moment of 3.18 B.M at 295 K. Suggest an explanation for these observations and
draw structures for the complexes, commenting on possible isomerism.

(4)

Conformational isomerism occurs if a metal complex can exist in two totally

different geometric forms. For example, [NiCl2(Ph2PCH2Ph)2] can interconvert
between square-planar and tetrahedral geometry.
P
Cl

Cl

Ni
Cl

Ni
P

P
P
Square-planar

Red, diamagnetic

Cl

P = PH2PCH2Ph

Tetrahedral

blue green, parmagnetic

Page 4 of 13

2.3

List any three (3) most commonly used techniques used to isolate pure products
from reaction mixtures.

(3)

Any 3 , 1 mark each

2.4

i.

Recrystallization of solid samples from solvent mixture

ii.

Sublimation of solid compounds

iii.

Distillation of liquid compounds

iv.

Separation by column or preparative thin layer chromatography

Predict with reason/s which of the following are labile or inert

(a)

[Co(NH3)6]2+

(b)

[PtCl6]2-

(c)

[V(phen)3]3+

(6)

Complexes with central metal atom having d electrons in the eg orbitals and
those that have less than three electrons in the d orbitals are labile. Thus
[Co(NH3)6]2+ = d7 and [V(phen)3]3+ = d2 are expected to be labile.

Octahedral low-spin d4, d5 and d6 complexes and octahedral d3 are all inert.
[PtCl6]2- = d6 , which means it is therefore inert.
2.5

Outline how K3[Rh(C2O4)3] can be prepared starting with K3[RhCl6]

K3[RhCl6] + 3 K2C2O4
wine red
2.6

2
(2)

H2O, 4 h
100 oC

K3[Rh(C2O4)3] + 6 KCl
yellow

Name the following compounds

(a)

(1)

1,1-diacetylosmocene

Page 5 of 13

(b)

(3)

dicarbonyl(5-cyclopentadienyl)(cyclopenta-2,4-dien-1-yl)iron

[25]

Question 3

3.1

Which of the following complexes would you expect to suffer from a JahnTeller
distortion: [CrI6]4-,[Cr(CN)6]4-, [CoF6]3- and [Mn(ox)3]3-? Give reasons for your
answers.

(3)

[CrI6]4-,[ and [Mn(ox)3]3 , both high-spin d4, thus the eg orbitals are unevenly
-

occupied and the complexes will therefore experience JahnTeller distortion

3.2

Using the crystal field theory, considering both the 4-coordinate and 6-coordinate
environment, account for the complexes that can be formed by the Co2+ ion.

(8)

Co2+ = d7 gives two types of four coordinate complexes, a paramagnetic square

planar complex in which there is a single unpaired electron and the dx2-y2 orbital
is unoccupied or a paramagnetic tetrahedral complex with three unpaired
electrons in the t2 orbitals, as depicted in the diagrams below.

dx2-y2

t2

dxy
dz2

dxy, dxz, dyz

dxz, dyz

e
dz2, dx2-y2

Co2+ (Square planar) 1

Page 6 of 13

Co2+ (tetrahedral) 1

eg

eg

t2g

t2g

Co2+ (octahedral, low-spin) 1

Co2+ (octahedral,high-spin) 1

The octahedral environment provides two types of complexes, in the low-spin

case a paramagnetic complex with a single unpaired electron is formed and the
high spin case a paramagnetic complex with in which there are three unpaired
electron .
3.3

If the colour of [Cr(NH3)6]3+ is red, what is the most likely colour of [Cr(CN)6]3-?
Is it red, yellow or violet? Explain

(3)

The metal is V2+ in both complexes. This is d3. CN- is a stronger ligand than
H2O andtherefore for [Cr(CN)6]4 is larger than that for [Cr(H2O)6]2+. The
CN complex looks yellow which means it absorbs violet light and the H 2O
complex looks blue so it absorbs orange light. Since the CN complex has a
larger , it will absorb a higher energy light (violet in this case). The H2O
complex has a lower and will absorb a lower energy light (orange in this
case).

3.4

Calculate the crystal field stabilization energies for Fe2+ ions in an octahedral field
and specify which of the two possible forms is more stable
CFSE = [6Dq (No. of e in the eg level)]+[-4Dq (No. of e in the t2g level)]
For Fe2+ = d6 both the low spin and high spin cases have to be considered
Page 7 of 13

(5)

CFSElow spin = [6(0)- 4(6)]Dq

CFSEhigh spin = [6(2)- 4(4)]Dq

= -24Dq

= 12- 16
= -4Dq

The lower the CFSE the more stable the complex. Thus low spin Fe2+ is more
stable than high spin Fe2+
3.5

List any three (3) shortcomings of the valence bond theory.

(1) variation of magnetic moment with temperature are not explained by VBT.
(2) Does not explain origin of colour in transition metal compounds

(3) Does not explain why some ligands give rise to high-spin and some to low
spin complexes

(4) Cannot distinguish two complexes with same number of unpaired electrons
but with different structures.

Any three will do

(3)

3.6

Account for the observed bond lengths in the following [Cu(H2O)6]2+ structure

(4)

The observed difference in bond length is due to Jahn-Teller effect. Cu2+ = d9 are
known to exhibit strong Jahn-Teller distortion.due to uneven occupation of the eg
orbitals. The distortion leads to tetragogal elongation whereby the ligands in the Z
axis move out and therefore interact less with those orbitals which have a z

Page 8 of 13

component ie the dz2, dxz and dyz and these orbitals attain lower energy. In the case
of tetragonal elongation this forces the odd electron to occupy the dx2-y2 orbital,
see below, resulting in increase in bond length of the axial bonds.

1
[25]

Question 4
4.1

[Ni(CO)4] is a highly toxic colourless liquid with low boiling point

(a)

What class of compounds does [Ni(CO)4] belong to?

(1)

Organometallic compound
(b)

Write an equation for the preparation of [Ni(CO)4]

o
Ni + 4 CO 25 C

1 bar

Fe + 5 CO
(c)

150oC
100 bar

(2)

[Ni(CO)4]
[Fe(CO)5]

Use valence bond theory to describe the bonding in [Ni(CO)4]

The oxidation state of Fe in the given complex is Ni(0)= d10
Page 9 of 13

(3)

Ni
3d

4s

4p

4s

4p

4d

Ni(0)
3d

XX

[Ni(CO)4]
3d

4d

XX XX XX

4s

4p

4d

XX = lone pair from CO

By filling the four electron pairs from the ligands to the metal ion gives rise to a
sp3 hybridazation which corresponds to a tetrahedral geometry. Since all electrons
are paired in the metals 3d orbital this corresponds to diamagnetic complex, hence
[Ni(CO)4] is tetrahedral and diamagnetic.
(d)

Explain why the complex is colourless

(1)
10

The metals d-orbitals are fully filled (d ), no d-d transitions, which are
responsible for colour, are possible.
4.2

Rationalize the following observations:

(a)

Explain why [Co(C5H5)2] is a good reducing agent while [Fe(C5H5)2]+ is

an oxidizing agent.

(2)

Cobaltocene is a 19-electron species and would thus be very likely to give

up an electron to achieve an 18-e configuration. On the other hand, the
ferrocinium cation is a 17-electron species and would thus be quite likely
to accept an electron to achieve an 18-e configuration.

(b)

From the IR spectra, the CO vibrations of [(PF3)Cr(CO)5] are higher than

those of [(PEt3)Cr(CO)5].

Page 10 of 13

(2)

PF3 is more electron withdrawing than PEt3, so the Cr center would be

more electron rich in the PEt3 complex. This leads to greater backbonding
to the CO's and weaker CO bonds for the PEt3 complex. Hence the (CO)
bands will appear at lower frequency in [(PEt3)Cr(CO)5.
4.3

Consider the following compounds

[Mn(CO)4(NO)], [RuCl(NO)2(PPh3)2] and [Co(NH3)5(NO)]2+
(a)

Using either the ionic or the covalent method show the electron count for
each of the given compounds above.

(b)

(6)

Draw the structures of the compounds clearly indicating the coordination

mode of the NO ligand.

(3)

(32)

NO linear
CO
Mn
NO

NO linear+ bent
-

= 8e
= 7e= 3e= 18 e-

Cl

= 1e-

PPh3

= 4e-

Ru

= 8e-

NO bent = 1e
NO linear = 3eTotal = 17 e-

(2)

Page 11 of 13

NO bent
NH3

= 10e-

Co

= 9e-

NO bent = 1eCharge = -2eTotal = 18 e4.4

Define or explain the following terms

(a)

Hapticity of a ligand

(1)

Hapticity of a ligand is the number of atoms that are directly bonded to the
metal centre
(b)

Coordinatively unsaturated complex

(1)

is a term used to describe a complex that has one or more open

coordination sites where another ligand can be accommodated
4.5

Draw the structures represented by the following formulae

(a)

PdCl2(2-C2H4)

(1)

(b)

[(ML2)3(2-Cl)3(3-O)]

(2)

[25]

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