COLLEGE OF CHEMICAL SCIENCES

Institute of Chemistry, Ceylon

Graduateship Examination in Chemistry 2019
Level 3
C 31053 SPECIAL TOPICS IN INORGANIC CHEMISTRY
DURATION: Three (03) HOURSplus L5 mins reading time
No. of Questions:S No. of Pages:09
Instructions:

(1) Answer AII Questions.

(2) The marks allocated to each question or parts of a question are indicated on the
right hand side.

(3) The questionpaper contains fourparts (A, B, C & D). The answers to all questions
should be submitted as per instructions by the chief examiner and these parts will
be collected separately.

(4) If these instructions are not followed correctly, l0 % of total marks will be
deducted as per college policy. The questions and the amount of marks they carry
are indicated below.

Question Marks
1 100
2 100
J 100
4 100
5 100

(5) Mobile phones not permitted

(6) The use of a non-programmable electronic calculator is permitted. However, the

memory on your calculator must be erased before you enter the examination hall.
 PART A

1. Answer all parts

(a) The fbliowing questions are based on the complexes (A to C) given below

Mo

(i) Calculate the total number of valence electrons of the complex A to C and show horv
you have arrived at the answer?
(ii) Calculate the formal oxidation states of the metal in each of the complexes A to C?
(iii) Calculate the true d' configurations of the metal in each of the complexes A to C?
(iv) What is the coordination number of the metal in the complexes A to C?
(30 Marks)

(b) Explain u'hy square planar d8 complexes are stable with 16 electron configuration and why
they only bind a frfth ligand weakly (to moderately). (15 Marks)

(c) Explain the following observations.

(i) The Co-P distance in [(q5 -CsHs)Co(PEts)z] is22l.9pm andthe P-C distance is 184.6
pm where as the corresponding distances in [(qs -CsHs)Co(pEtl)z]* are223 pm and
782.9 pm.
(ii) on forming [IrBr(co){q2 -cz(cN)+}(pp}u)z], the unique c:c bond in cz(cN)+
lengthens from 135 to 151 pm.
(iii) The Tolman cone angles of PPhr and P(p-MeCoH+)s are l45",where as that of p(o-
MeCoFI+)r is 194o.
(iv) [Mo(PMer)sHz] is a di-hydride (contains two separate H ligands), but
[Mo(CO):(PR.:)z(Hz)] contains the dihydrogen ligand (Me : methyl, R: isopropyl).

(40 Marks)
(d) Identifu the following complexes as a Fischer carbene or Schrock carbene? Explain your
answers.

PCya

(15 Marks)

PART B

) Answer all parts

(a)
(i) Propose plausible catalltic cycles for the following reactions:
(ii) Identify the type of organometallic reaction in each ofthe steps involved in the catalytic
cycle.

I.

Catalyst
+ HC:.H -
Mo(Co)6

II
o
lt Catalvst
cH3cH2cH2C-H +
HC"A|GRT) t"'t'2cH2cH2oH
H2

(50 Marks)

(b) Predict the fiaal products A, B, c, D and E of the following reactions.

(i)
PPh3
A (l8e neutral complex)
(Hint: 2 step process)

-+'
 (ii) ocl ,PPh3
\ ,/ Na+
-ocH2cH3 B (16e neutral complex) + C (Organic proc
,/'\
Ph3P tr (Hint: 2 step process)

A
p-hr* D (16e neutral complex) + E (Organic product)
(Hint 2 step process)
(20 Marks)

(c) Give reasons for the following observations.

(i) I0ft-CrHs)Ir(PMer)Etl* is unstable compared to [(4r-CsHs)Ir(dmpe)Et]+.
(dmpe: (CH:)zPCFIzCHzP(CH:)2, Me: CH3, Et: CzHs
(ii) The reductive elimination of Hz observed with the compound (PPh:)sIrCl(H)z can be
suppressed by replacing PPhr with P(CHr):.
(Ph: CeHs) (10 Marks)
(d) Write an acceptable mechanism for the following reaction. trdentify the steps involved.

CH2:CII2
+ CII3CH=CH2 + CHa
PPhr
rr3 GHs Phs

(20 Marks)

4
 PART C
3. Answer all parts

(a) (i) State the selection rule for a vibrational mode of a molecule to be IR active.

(ii) Sketch possible IR active vibrational modes of HzO and identify the vibrational modes.

(iii) (A) and (B) are two possible structures for [r1s-csMes)zFez(co)+].

(A (B)

By using the FT-IR spectra of nujol (Figure-1) and [4s-CsMe,)zFez(CO)a] (Figure-2) given
below, identiff the correct structure for [4s-C5lvles)zFez(CO)+]

Figure 1

2800

r {'1
sno 20m

(25 Marks)
 (b) (i) The structure of BrFs is given below.

When the temperature is > 450 K the BrFs molecule shows fluxonality on the Niv{R time scaie.
Predict and draw the leF NMR spectrum of BrFs under follorving conditions.

(r) At 480 K
(li) At room temperature

Note: No coupling to Br nucleus occurs

(ii) Predict and dras,the 118-NMR spectrum of the follou,'ing two complexes.

(D ,O'+BHs

(II) phMe2p+ BH3

(l'{ote; Ifor3lP: Yr; Jey> Jr:u)

(iii) How u.ould you identifl, the following trvo isorners by rtp NMR spectroscopy.

PMe3 PMe3

PMe3

(D (ID
(45 Marks)
(c) Determine the structures of PCl:Fzand PCIzF: by using the NQR and NMR data given below.

3scl leF
R AvIHz NMR
PCl:Fz 31.57 - 123.0
PClzFs 3t.49 - 67.4,+ 41.5
(30 Marks)
4. Answer all parts.

(a) (i) Briefly explain the following terms with reference to charge transfer transistions. Give an
example for each.

(I) Ligand to metal charge transfer

(II) Metal to ligand charge transfer

(ii) "The value of €ma,r of the most intense absorption band in the electronic spectra of
tetrahedral [CoCl+]2- and octahedral [Co(OHz)el2* differ by a factor of about 100,,.
Comment on this observation and state which complex would exhibit the larger value of
cI'maX.
(35 Marks)

(b) (i) what is meant by the term "Hyperfine splitting in ESR" spectroscopy?

(D Draw a suitable diagram to show what happens to the spin energy level of an
unpaired electron present in a paramagnetic material, when it is placed in a
magnetic field,

(ID Sketch the energy levels of deuterium arising due to Hyperfine coupling. Indicate
allowed transitions.

0[) Predict the ESR spectrum of deuterium

Q{ote: Ifor Deuterium is I)

(ii) The ESR spectrum of a radical having a single magnetic nucleus shows four lines of equal
intensity. Calculate the spin of that nucleus. (35 Marks)

(c) (i) What are the factors affecting the isomer shift with respect to Mossbauer spectoscopy?

(ii) Label the isomer shift and the quadnrpole splitting (AEd in the Mdssbauer specrrum
given below.

c
6
'd

cG
F

Velocity (rnrn/s)
(30 Marks)

7
 ART D
5. Answer all parts

(a) Predict the number of absorption bands given by the following complexesicompound

(i) FeCl: (ii) KMnO+ {iii) ZnClz (15 Marks)

(b) One of the following UV-visible spectra- belongs to [Cr(HzO)]3* ion and other one belongs to
TiCl.r-.

Spectrum A - 8000 cm-r. 15500 cm-l, 23500 cm-l

Spectrum R - 8000 cm-r,23000 cm't,41500 cm-I
(i) Giving reasons, select the correct spectrum for the given ion [Cr(HzO)]3*. (20 Marks)
(ii) Use simplified Orgel diagrams to explain the above mentioned bands in both complex
ions.. (40 Marks)
(iii) Conment on the approximate molar absorbance (e) expected for the selected spectrum of
TiCl+- (10 Marks)
(iv) Calculate the Racah parameter and Nephelauxetic ratio B, if the experimental B value is
980 for Cr and 965 for Ti. (15 Marks)

8
 'I

H
2
Peri ilic Table of the Elements
't3
He
1

5 7 I T;'
Li B C N o F Ne
11 12
t,l l6 '11 1A
Na Ms AI Si s cl Ar
5 7 1)
19 20 ?7 A. ?5 21 as 30 31 32 13 35 l€
K Ca Sc Ti v Mn Fe Co Ni Gu Zn Ga Ge As Se Br Kr
18 9p 40 at t2 ,it 45 1T l6 52 s 54
Rb Sr Y Zr Nb Mo Ru Rh Pd Ag cd 5n Sb Te I Xe
55 50 5770 71 73 T4 1& 75 77 7t 70 8i 81 g7 83 41
Cs Ba I Lu Hf Ta w Re Os lr Pt Au Hg TI Ph Bi Po AT Rn
87 s0 lst{02 103 10r 10s 107 108 to! 'll o 111 112 113 111 115 ,16 117 118
Fr Ra I Lr Rf Db Bh Hs Mt Ds Rg Uub Uut hrr JU LJu lut
(ttui 12iE i2!

57 5E sg 60 6t 64 63 s
52 fr 6S 70
La Ce Pr Nd Pm sm Eu Gd Tb Dy Ho Er Tm Yb
g0
00 9t 92 9A 9l 95 si 97 .96 9o 100 101 102
Ac Th Pa U Np Pu Arn Gm BK CI Es Fm Mcl No