2

PONDICHERRY UNIVERSIY
DEPARTMENT OF CHEMISTRY
CHEM 423: Structure and Spectra-Mag'etieResonance
2023
M. Sc. Chemical Sciences, End Semester Examination, August
Maximum marks 60
Tihe: 3 hrs or Bfrom Each question
Answer all questions taking A
information about the connectivity and
1A|How does the J-coupling constant provide [4]
) conformation of neighboring protons in NMR spectra?
including spin-lattice relaxation (T1) and
Explain the concept of relaxation mechani_sms in NMR, [4]
molecular dynamics.
ii) spin-spin relaxation (T2), and how they are influenced by
how it provides insight into transition
Explain the concept of zero-field splitting in EPR and (4]
metal complexes' electronic structure and coordination.
OR
exchange in NMR spectroscopy and how it
contributes
1B Describe the phenomenon of chemical [4]
io multipie resongACes in some instances.
the EPR spectra of transition metal ions, and
What is the role of the ligand field in determining [4]
contribute to this?
how do crystal field and molecular orbital theory
and their catalytic
How does EPR Spectroscopy
contribute to the study of metalloenzymes
application in this context? [4]
mechanisms, and provide an example of its
hydrocarbon compound.
oneF atoms present in ahalogenated
2A|There are one CI, two Br, and molecular ion and the corresponding isotopic peaks in the mass
i) What would be the ratio of the (2]
spectrum?
methyl
distinguishing between 1-propyl ethanoate and
Explain how mass spectra can help in [2]
butanoate.
cyclohexene from
not be a good way to distinguish
Explain why mass spectrometry might [2]
ii cyclohexanol.
mass 57 is formed in
fragmentation within a mass spectrometer, one mono positive ion of ion (m/z = 57) is
In a the same
another identical fragmentation
the ionization chamber and in an these two ions would have higher kinetic energy? [2
formed in the analyzer tube. Which of these mass
ions observed in
reactions to account for the following
Give logical fragmentation (4]
V) spectra.
55 b. 3-methylpentane: 86, 71, 43
a. 3-methyl-1-butanol: 70, mass spectra of 1
for the base peak (m/z =31) in the
What do you suggest as a structure
2B
(21
i) butanol? produces a
mass 100 undergoes fragméntation in the analyzer chamber and the mass
mÍther Ton of ion in
If the the m/z position of this daughter
daughter ion of mass 60, what would be (21
spectrum? observed in these mass
to account for the following ions
Give logical fragmentation reactions b. methylcyclohexane: 98, 83 [4]
spectra. a. 1-pentanol: 70, 55, 41, 31
2

values, 183, 169.

36 saturated hydrocarbon (MM = 212) shows four characteristic peaks at m/z
0v) A of the molecule.
[4]
155 and 141? Draw the structure

32J

)344
CHÝ

3A
Determine the numberof different kinds of protons in the following
(a) 2,2-dimethylbutane (b) 1-bromo-2-methylbenzene
compöugds?
Using a 60 MHz spectrometer a chemist
3.4 ppm. observes the following absorption: Doublet, J=7 Hz at
(I) How many Hertz from the
() Predict this proton's
TMS peak in this absorption?
chemical
(II) What would the Jvalue in the shift (in ppm and in Hertz) at 100 MHz.
100 MHz spectrum?
ii) Draw formulae for all the isomers of
intensities in their H-NMR spectra. dichlorocyclopropane
and predict the relative
signal
[6
3B Are the OR
hydrogens in the following molecules homotopic,
enantiotopic or diastereotopic? (2]
CH, H
CH, CH,CH, CH, CH,
CH(CH)2
H
H
ii) Assign the following H
rule to predict the chemical shiftsto the hydrogens in the
multiplicities of the peaks. following compound. Use the (n+1)
iv) How many signals will be
the chemical shifts of there in the H NMR BrCH,C H2CH2Br. 6H 3.59, 2.36
(2)
the signals. spectrum of each of these
MeG
OMe
compounds? NO2Estimate
[4}
Me,N

b
iv) The 'H NMR d
spectra for the following
below. Assign the
A:5 1.54 (s \ structures.
D:6 1.20-1.70 B:6 5.74 (s)W
eight-membered ring
compounds (A-D) are
C:8
(m,4H), 1.85-2.50 (m, AH),2.39(m,8H), 5.60 (m, 4H) summarized[4]
5.35-5.94 (m,4H)

iv Ce-ce

a
-\+
4A ldentify the folowing cormpound from the given molecular formula, chemical shifts in RA and
(2]
multiplicity offthe pfoton koupled 19C NMR spectrum.
CsHtsO: õc 712,t 33.1, t
20.3, t 14.6, q
61.1, 100-150 ppm (four
The CNMR spectrum for ethyl benzoate contains these peaks: 17.3, (4]
peaks), and 166.8ppm. Which peak belongs to which carbon atom?
compound with molecular formula
The 13C NMR, DEPT-135 and DEPT-90 spectral data for a [6]
CAH6 are shown below. Draw thestructure and assign the peaks.

|Normal Carbon DEPT-135 DEPT-90

Normal Carbon DEPT-135 DEPT-90
Negative No peak
85.5 ppm No peak No peak 12.8 ppm
Positive 12.4 ppm Positive No peak
67.1 ppm Positive
H{cHCEH HC
OR

spectrum for 2-butanone contains these peaks: 7.5

4B The off-resonance decoupled C NMR
(singlet) ppm. Which peak belongs to which
i) (quartet), 30.1 (quartet), 37.2 (triplet), and 209.2 2
carbon aiu?
C4H802, the 1H NMR appears as 3.60 ppm (s, 3H),
For acompound with the molecular formula O
3H) and the 13C NMR signals appear at 174.6,
2.41 ppm (qr, 7.5 Hz, 2H), 1.21 ppm (t, 7.5 ofHz,the molecule, assign the peaks and then draw
51.9, 27.3 and 9.4 ppm. Draw the structure [4]
HETCOR 2D NMR diagram for the compound.
sample is needed and why? When ethyl acetate is
In which NMR, Hor 13C, alarger amount of singlets and a triplet
data is collected, four
dissclved in CDCl3 and a proton decoupled 13C NMR Assign all the peaks. If the
ppm respectively.
appear at 170.2, 61.0, 20.7, 14.1 and 77.0, concentration and height of the solution
diameter of the NMR tube is increased keeping the [6]
constant, what would happen to the signal intensities?
and assign all the peaks from
5A Draw the structure of the compound from the following spectra
[12]
all the spectra.
H9.15;Q36.32 Mass: 132, 117, 75, 43 IR: 1715, 2900 cm
Elenental analysis: C54.53,
yGMR: 54.8 (t, 8Hz, 1H)/3.4 (5, 6H), 2.7 (d, 8Hz, 2H), 2.2 (s, 3H))
A3C NMR: 6 205.1, 101.8, 53.7, 47.5, 30.8
OR ot.
5B The spectroscopic properties of a high-boiling liquid (b. are given below. Draw the C 3 .
structure from the following spectra and assign all the signals from all the [121
IR: 1620 cm,1695 cm1., Mass (% of intensity) : m/z 43(78), 55(100), 83(90), 98(49, MMM)
'H NMR (90MHZ):61.9 (3H, s), 2.1 (3H, s), 2.2 (3H, s), 6.1 (1H, s)
13CNMR:6 20.1, 27.2,31.1, 124.3, 154.1 and 197.2
12y t 2
|2Y 3 6
9

o
 PONDICHERRY UNIVERSITY
Department of Chemistry
Organometallic Compounds
AM 424: Structure and Bonding in Coordination and
of Transition Metals
End Semester Examination, 7th August, 2023

Max. Marks: 60
Duration: 3h
Answer AllQuestions

Unit I
optical activity;
and tams isomers of (Colen)2Cl2l and comment on their 4M
(a) Draw (1) cs octahedral complex of [Co(NH3)3Cls]?
(ii) fac and mer isomers for an arrangements/isomers is stable?.Why?
following
{which cne fromcach sct of the 4M

i. [Pt(NCS)2(PRs)2] and (Pt(SCN)2(PRs)2] -FellLCN-Crill NC-Fell-CN-CrlILL

-Fell-NC-CrlIL-CN-Fel_NC-CrlIl and
i. 4M
and A enantiomers from the structures given below.
(c) Identify the A

= en

following complexes and include coordination symbol

for the
2. (a) Write IUPAC names wherever applicable.
4M
and configuration index
ii. trans-[CoCla(NH3)4]C1 ii. fac-[Fe(CNCH3)3Bra]
i. cis-(Pt(py)2(NH3)2]Cl2
iv. (Ru(bpy)zlacac)|PF6]2
4M
suitable CD and ORD plots.
(b) Explain Cotton effect using order of increasing ability to form
stable
following six ligands in
(c) Arrange the 4M
complexesand account for your order.
 NH HN, -NH HN
H,NNH
NH, HN -NH2 HN
A B C

NH HN

H,N NH2 NH, NH,

NH HN
D
F

Unit I

3. (a) Explain the trends in ionic radii given in the

plot applying crystal field theory.
4M
100J
- 34 26
904

80

70

60
igh spin
low spia
50

Ti V Cr Mn Fe Co NI Cu ZA
M: Sc Ti V C Mn Fe Co Ni Cu G
0 1 2 3 4 5 6 7 8
9 10
Ouber ofdelectrons
(b) For each of the following
pairsof
and show how you worked it out.complexes, identify the one that has larger LFSE
() V(OH2)6|3+ or 4M
[V(OH2)6|
(i) [Mn(OHa)6]2* or
2*
[Fe(OH2)6|3*
(ii) [NiCl42 or [Ni(CO)4] 411
(iv) [Fe(CN)6|3- or (Ru(CN)6|3
 the following OX1des
Assuming CFSE is the deciding factor predict the structures of 4M
in terms of normal or inverse spinel. Justify your answer.
a. MngO4 b. NiFe204 c. MgAlzO4 d. Co3O4

or

field theory explain the magnetic properties of the following

tya) Using crystal 4M
complexes.
a. (PtCl4]2 b. [NiCl4j2- c. [CoFs]3- d. (Co(NH3)6]3* the
of the following ligands in
orbital theory explain the order 4M
(b) Based on molecular
spectrochemical series. F<NH3 < PPh3.
Justify
complexes based on C-O bond stretching frequency.
(C) Arrange the following 4M

(Ti(CO)s|2- d. [Mn(Co)sj2*
a. [V(co)s] b. [Cr(Co)s] c.

Unit III

following ions.
Compare the extinction coefficients ([, in UV-Vis spectrum) of the
5. (a) for [ that you have predicted. 4M
Explain why these ions will have the magnitude
(Cr(NH3)6]3+
i. [MnO4] ii. (Mn(H0)6]2* ii. [NiCl4j2- ii.
4M
unstable?
(b) Why is Fel; thermodynamically
[Fe(CN)6]3- and include o, n
(c) Construct molecular orbital diagrams for [FeFs]3- and A, is the energy
and non-bonding electrons. Explain why for T-donor ligands
the energy
separating between tag* and eg*, while for racceptor ligarnds A, is 4M
separating between tag and eg.
Or

6. (a) Depict n overlap ofa metal d orbital with various types of ligand orbitals and give
4M
an example of ligand for each type.
(b) Explain the order of C-Oax stretching frequency in the following complexes. 4M
CH=CtcH
 Wh
w ahi
tl l

(i
F )e(c

w(co)s(PF) (2007 cm-!) > W(Co)s(PCl) (1990 cm') >Ww(CO)s(P(OPh)a) (1965 cm

n bond between W (P
) r
> W(CO)s(PPh3) (1942 cm-)and comment on the strength of the
and CO ax.

(c) Show the possible d-d transitions in the following complexes. Also comment
4M
whether they undergo Jahn- Teller distortion or not.
i. [CoFo]3 ii. (NiCl]2 iii. [v(OH2)6]3* iv. [Cu(NO2)6]
Unit IV

7. (a) Predict the molecular structure for the following complexes. 3M

(0) (Cr(cO)3(Cycloheptatriene)] (ii) [CpCo(cyclo-octatetraene)] (ii) [CpFe(C7H7)(CO))

(b) Predict the products for. the following reactions. 3M

(i) Mn2(CO)10 reaction with Na/Hg followed by Mel

(ii) W(CO)6 reaction with NaCp followed by EtI
(ii) CpFe(CO)2l- reaction with MeCOc1 followed by light
(c) Predict the products for the following reactions. 3M

(i) Cp2Ti(Me)2 reaction with light followed by CO

(ii) Cp2Ti(Me)2 reaction with light followed by S8
(iiü) Cp2Ti(Me)2 reaction with light followed by PhCCPh
electronic structures for the following
(d) Explain the products formation and 3M
reactions.
cyclohexene in the presence of Na/Hg
(i) (Pt(PPhs)4] reaction with 1,2 dibromo
followed by light
(ii) (CpMo(CO)3] reaction with BnCl
Or

[W(CO)s(C(OMe) Me] is relatively more stable than [W(CO)s(CMez) and

8. (a) Explain why these compounds.
3M
provide a method to make
3M
reactions.
(b) Predict the products for the following
(i) (CpRe(C(0)Me) (PPhs) (NO)] with HOTF
(i) (CpRe(NO)(L) Me] with Ph3C+PF6
en W
What will happen when you
shine light on the
(1) Fe(CO)s (i) following complexes? 3M

(d) Predict the [Mn(CO)s(CH2CH2CHCHa)] (ii) CpCo(CO)2

products for the following reactions. 3M
(1) PaCl42 with
CH2CHCH3 Pd with PhCH,C1 (iiü)
(ii)
[Cplr(CH,CHCHCH2)] with HCI/CO
Unit IV
9. (a) High spin Fe(ll) is too large to fit intothe
porphyrin ring, but low spin Fe(l) can be
accommodated. Why does the high spin ion has a larger radius? 2M
(b) Carbon monoxide is well known to be a strong
inhibitor of O2 binding by myOglobin
and haemoglobin, yet relative to O2 its binding is much weaker in the protein
compared to a simple Fe-porphyrin complex. This.suppression of. CO binding is
important as even trace levels of CO would otherwise have serious consequences
for aerobes. Suggest an explanation. 2M

(c) Depict the structure of cytochrome cand explain the sequence of electron
transfer reactions towards oxidative phosphorylation. 4M

(d) Explain the strueture and function of transferrin and ferritin in biological systems
using descriptive diagrams. 4M

Or

J6. (a) Why would the substitution of Mg2+ or Zn2+ for the Fe2+ hinder the function of
cytochrome. 2M

(b) Match the following: 2M

(i). Heme protein (A). Transferrin

(ii). Iron-sulfur protein (B). Hemerythrin
(ii). Cu containing protein (C). Rubredoxin
(iv). Iron storage system (D). Cytochrome
(E). Hemocyanin
(F). Ferritin

(c) Draw the diagrams of various Iron-Sulfur proteins and explain their role in
biological systems. 4M

(d) What are Siderophores? Explain their structural features and functional aspects.
4M
 ) B77

Pondicherry University
School of Physical, Chemicaland Applied Sciences
Department of Chemistry
MechanismLAU2
END Semester Examination - August 18, 2023
GHEM 421: Reaction Kinetics and
Max. Marks: 60
Max. Duration: 3 h
Answer ALL questions
Unit-I
reaction and its significancé.
1(a). Describe stopped-flow technique for studying fast (3)
(2)
1(b). Diferentiate the terms free energy and activation energy. (3)
1(c). Showthat Hammett equation follows LFER. suitable diagram. (4)
1(d). Discuss the consecutive complex reaction with a
constant and equilibrium constant from
1(e). Derive the relationship between the rate theory. (3)
absolute rate theory and write the significance of this
(OR)
for studying fast reaction. (3)
2(a). Describe laser flash photolysis technique (2)
2(b). Define the term alpha effect with examples. (3)
of acids and bases.
2(c). Briefly discuss Bronsted-Lowny concept
2(d). How do you propose the mechanism of the reaction between H2 and Brz (4)
isotopic effects with examples. (3)
2(e). Discuss the kinetic
Unit-I|
reactions with suitable mechanisms. (3)
3(a). Find out the product for the following
ii)
i)
HCI
MeOH

with suitable mechanisms. (3)

3(b). Write the major product of the following reactions
ii)

Br 1. NaOH, H,o Ph NMe2 1. PhMgCI

LBr 2. HCI, H,0 2. H,SO

adiact ot ore
1
 3(c). i) Write a shot note on SN reaction with suitable examples.
i) Write the major product of the following reaction. (3)

CO,H 1. NaNOz, HCI, 0 °C

NH2 2. Benzyne

3(d). Suggest a suitable mechanism for the following reactions. (3)

i)
-cO,H

NaHCO

Br
i)
Br, H,0
HO
NMe Me
3(e). Write the major product of the following reactions with the suitable
mechanism. (3)
OEt i)
i) HNO3 AICI,
i)CH,0, HCI,
ZnCl,

(OR)
4(a). ldentify the major product of the following reactions. (3)
i)
OH SO,CI i)Pyridine
i) Bu,N*CH,CO,
DMF

ii)
Br
i)NaNH2, Liq. NH3
i) CH(CO,Et)2

2
 4(0). Find out the major product of the following reactions with
suitable mechanisms. ()

EtOH
ii) HO, i) CH,SO,CI
Pyridine
Me,
Br ii)KCN, DMF

4(c). Explain E1 &Ez-Elimination reactions with suitable examples. (3)

4(d). Taking phenolas the starting material, explain the step-wise synthesis of the
following compounds. (3)
ii) OH
OCH,
CI

HN

4(e). Find out the products A, B, and C with step-wise mechanism. (3)

i) ii)
1. Me,Culi, 1. H,0*
2. Me,SiCI 2. Mel
NEt A Me

Unit- I|I

5(a). ldentify the structure of product with correct relative stereochemistry formed in the
following transformation. (2)
OBZ
OTBS

ÔMe

5(b). Prove that the [6+4] cycloaddition is allowed under thermal condition using Dewar
.Zimmerman approach. (2)

3
 5(c).The following transformation is successful with help of two key pericyclic reactions.
ldentify those reactions and explain them mechanistically (3)

SiMe
TBAT
OTE
TBAT =Tetrabutylammonium triphenylsilyldifluoride

5(d). Predict the product formed in the following

involved. transformations and explain the steps
(3)
-PrO

iPro [B]

5(e). The transformation of

sequences from B goingisopulegone to E involves multiple pericyclic reaction
via C and D. ldentify the structures
of A, B, C, D and E.
(5)
wOTBS 1. KH, Allyl bromide (Gives B)
[A]
2. MW, 210 °C, Toluene [E]

(OR)
6(a). Explain using
Woodward-Hoffman rule that why suprafacial [1,5]-hydrogen shift is
thermally allowed?
(2)
6(b). Write the structure of product
steps involved. formed in the following transformation and
explain the
AICI,

6(c). Mechanisticaly explain the following transformations.

(3)

hv
A 55 °C, 14 h
OAc aq. MeOH (2 steps)
X2 10°c R1
X OAC
6
 correct stereochemistry in the following
6(d). ldentify the structurels of product/s with (3)
transformation. Justify your answer.

COOMe
ZnClh, 25 °C

H reaction between 1,3

correlation diagram that the cycloaddition (5)
6(e). Prove using favored thermally.
butadiene and ethylene is
Unit V
biological acylating agent. Explain
CH3COSA) is the carbon
(CH3COSH / and odd numbered
7(a). Acetylcoenzyme
coenzyme in building even numbered
fatty acids and terpenes.
(5)
the role of acetyl of various
biomolecules like
framework for the biosynthesis the compound whose
the formation of
biosynthesis of tryptophan involves reaction is indicated by the arrow,
7(b). The in the carbon.
The new bond formed configuration at the anomeric
structure is shown below. retention of compounds
proceeds with two starting
and the reaction released. Show the structures of the (5)
Inorganic pyrophosphate is the reaction(s).
mechanism of
A and B. and
co
NH
A+B new bond
inorganic pyrophosphate
H OH

pyruvate an three carbonalpha keto carboxylate.

product in Glycolysis is oxidation of glyceraldehyde - 3 phosphate to 1,3
7(c). The final steps involve addition to NAD+ and
One of the intermediateThe overall transformation involves, in in Fig.1. From
bisphosphoglycerate.
catalyst. The structure of NAD+ is given
mechanism for all
enzyme as
phosphate, cysteine inhave learnt in other units of this course draw
cysteine. (5)
the mechanisms you 1,3-bisphosphoglycerate. Use the notation Enz-Cys-SH,
reactions leadingto
Glyceraldehyde-3-phosphate
OPO,2
Dehydrogenas"
H NAD NADH

Hz¢-OH
+ Pi He-oH
3CHzOPO,2 3CH,0PO,?

glyceraldehyde
3-phosphate óH OH Fig. 1
 (OR)
8(a). In laboratory organic chemistry
moderate nucleofugal leaving group ispractices, the hydroxyl group in alcohol, which is a
into a mesylate or tosylate or triflate. activated as a good leaving group by converting it
What is the analogous reaction in Describe the principle involved in alcohol activation.
biological reacion? Write the reaction with
mechanism.
8(b). In Fig.1 in Question IVA, if (3)
display red-ox property as NAD pyridine is replaced by
+/NADH. Justify your benzene, will the resulting system
8 (c) Busulfan answer. (3)
(Fig.2) is used in cancer
clipping the two strands of DNA treatment.
double
The compound acts as
alkylating agent
mechanism alkylation by busulfan and
of helix by
clipping ofalkylating guanine
the double helix. units (Fig.3) Write
(3)
Base

Phosphates

OH
Fig.2 Sugar

8(d). Pyridoxal Fig.3

to alpha amino phosphate
acid and
is the cofactor that
mediates the conversion of
as trans
amination. oxidation of amino acid to alpha keto acid by the alpha keto acid
reactions you Lysine in enzyme plays an process known
and pyruvate tolearnt this course write mechanism
in important
for
role in this process.
From the
alanine. conversion of alanine to pyruvate
Ho (6)
OH
HO OH

H,0 HC
alanine
NH3
pyridoxal pyruvate

-END
 PONDICHERRY UNIVERSITY

Department of Chemistry
CHEM 424: Structure and bonding in coordination &organometallic compounds
of transition metals

SESSIONAL EXAMINATIONII
Maximum Marks: 30
Time: TwoHours N
Answer All the Questions

PART-A (5 x3=15 marks)

structure of the products.

Predict the product for the following reactions and explain the
() {CpRe(NOPPia)C(O)M)]vith CF:SO;H
(i) CpMn(CO)TH reaction with CHN,
2. How will you prepare the following?
[Cp2Ta(Me)2]* with NaOMe
() [CpFe(CO)Me] from [CpYe(CO)2] (i)
following reaction
3, Predict the products and structures for the
(Mn(CO)s(CHCHCH»)] with light
() 2eq. of [CpCo(CO)2] with light (ii)
FeCp: and8 interaction.
A. Explain the nature of FMOs of structure of the products
following reactions and discuss about the
5. Predict the products for the 25 °C
CpCo(C2H4)2 + 3MeCHCHMe (ii) Coz(CO)8 with BuCP in THF at
(i)

PART-B (15 marks)

your answer. (2 marks)
important bulk & trace metal ions and justify
1. Write the biologically
condition. (2 marks)
inhalation of large quantity of CO leads to fatal
2. Explain how the
oxymyoglobin and oxyhemoglobin using equations
3. Explain the formation of
(3 marks)
curves.
and oxygen binding
hemocyanin interms of their
Compare and contrast the hemerythrin and
4.
(4 marks)
aspects.
structural and functional
hemoglobin and illustrate the
the structural features of myoglobin and
5. Explain
(4 marks)
Perutz mechanism.
Oxygenation properties using

6
 2-4
|2
2 DEPARTMENT OF CHEMISTRY
PONDICHERRY UNIVERSITY, PONDICHERRY- 605 014
CHEM424- ADVANCED INORGANIC CHEMITRY-I|
FIRST SESSIONAL EXAMINATION - July 11th, 2023
Time: 2h Max. Marks: 30

lWrite IUPAC names of the following complexes and include coordination symbol and
4M
configuration index wherever applicable.
i. trons-[Co(en),Cl(NO:)]CI
i. foc-(Colen)Cl(NHa)j]CI iv. [Ru(bpy)al[PFs]3
i. NasfAl(C204)3]
2. For each of the following pairs of complexes, identify the one
that has larger LFSE and
5M
show how you worked it out:
(i) [Cr(OH2j6]* or [Mn(OHa)6]2* -6 = - 3
(ii) [Mn(OH2)6]* or (Fe(OH:)6j
) [Fe{QH:)t or Fe{CN)613
(iv) (Fe(CN)GJ³ or [Ru(CN)6]3 [CoCl4]2
(v) Jatrahedral [FeCl4] or tetrahedralpredict the structures of the following oxides in
3ASSuming CFSE is the deciding factor, 4M
answer.
termsof normal or inverse spinel. Justify your
C. Co304 d. CoCr204
a. ZnMn204 b. Fe304
oxidation state
Expiain why metal carbonyls with metal in low oxidation state or zero
4. oxidation state.
3M
metal in high
are more stable than those with imaginary
diagrams for [CoF6] and [Co(PPhsle]* (an
5. Construct molecular orbital non-bonding electrons. Explain why for -donor ligands
complex) and include o, n and the
ligands A, is
tzg* and e, while for I-acceptor
Ao is the energy difference between 5M
energy difference between t2g and eg*. following
the relative extinction coefficients ([, in UV-Vis spectrum) for the
6. Predict
magnitude for [ that you have predicted.4M
the
ions.Explain why these iors willhave (Cr(NH3)6]3*
i. [MnO4] i. [Mn(H,O)%|2+ i.
complexes having
Classify the fallowing configurations as A, E, or T(degeneracies) in
7. 3M
Oh symmetry. vi. e,
i. tag'e,? ii. t25 ii. tgPe iv. tzg;a v. e'
transfer
and {MnO4] all have intense charge
8,The isoelectronic ions [VO4], [Cr04] transitions increase in this series, with [MnO4]
transitions. The wavelengths of these
longest wavelength. Suggest a reason for
having its charge-transfer absorption at the 4M
this trend.
Predict which of the following cpmpfeyes ugdergoJahn-Teller distortion. 2M
9. b. [Cu(CH3CN)4|PFo c. [Co(NHa)6] Cls d. Kz[FeClkl
a. Ka[CrCl)

3/5 (6.
 PONDICHERRY UNIVERSsITY
DEPARTMENT OF CHEMISTRY
CHEM 422: STRUCTURE AND SPECTRA: ELECTRONIC VIBRATIONAL,
MICROWAVE
M. Sc. Chemistry, End Senester Examination, August 2023

Answer all questions choosing either of the set of questions from each unit. Mixing answers from between
the sets is not allowed.

Unit 1 (4 marks each)

1. How does the theory of normal vibrations relate to electromagnetic radiation and its interaction
with matter?

2. Could you elaborate on the quantum mechanical approach to transition probabilities and how
they connect to Einstein coefficients?
3. What are the key components of pure vibrational and rotational spectra in molecular
spectroscopy?
(OR)
spectra of polyatomic
4. How do selection rules play a role in determining vibrationaland rotational
molecules?
they're used in understanding
5. Can you explain the concept of projection operators and how
normal modes of vibration?
vibraticns, and how does it influence
6. What is the significance of anharmonicity in molecular
spectroscopic behaviour?

UNIT II (4 marks each)

electronic transitions, and how are they
7. How are transition moments crucial in understanding
related to the concept of dipole moments?
the assignment of electronic transitions in
8. Could yuu explain how group theory is employed in
molecuies like Nz, H,0?
phosphorescence, and how do they relate
9. What are the key differences between fluorescence and
to the relaxation of excited states?
(OR)
and how do they impact the
10. What factors determine the selection rules for electronic transitions,
observed spectroscopic behaviour?
transitions in complex
11. Could you provide insights into the process of assigning electronic
molecules using group theory?
they
12. Can youdescribe how fluorescence and phosphorescence processes occur, and how are
related to the lifetime of excited states?
UNIT II (4 marks each)
band in the infrared? What are the full
13. Why is the O-H absorption of CH3COOH ch a broad
forms of ORD and CD?
stretching
14. Which of the bonds between the marked atoms are expected to have IR active
frequencies?

(a) H-=-H b. H-C=@-ic. HC-=-CH, (d) H,C-CH,

15. Use the Woodward-Fieser rules to predict the Amax value forthe following structures. (A values
for parent cisoid =253 nm and transoid =214 nm; double bond extending conjugation =+30 nm,
alkyl substituent/exocyclic double bond =+5 nm)
ÇH, Me C,H
Me
B

CH,

(OR)
16. How is the O-H absorption peak shifted by replacing the Hwith a D? The 0-H and O-D bonds
have
approximately the same bond strength (force constants) Acetic anhydride shows two C=0
absorptions in IR spectroscopy. Why?
17. (a) Explain which of the three carbon-nitrogen bonds in the following
in the infrared at the largest wavenumber.
compound willabsorb light

CH,-C- N-CH=CH,
CH,
(b) For which isomer, cis-stilbene, or trans-stilbene, the T> T* transition occur at a longer
wavelength with a higher extinction coefficient?
18. What would be the Cotton Effect (+ or -)for
compound has a specific rotation of +5°. What is(2R,3S)-2,3-dimethylclohexanone?
Assume that this
the optical purity of a mixture of the two
enantiomers of this compound whose specific rotation was found to be -2°? What is the %
composition of the mixture?
UNIT IV (4 marks eoch)
properties of
applied to analyze the electronic and vibrational
19. How are spectroscopic techniques element nature influence their spectra?
diatormic molecules, and how does the p-block
and
elaborate on the application of spectroscopy to analyze the vibrational modes
20. Could you elements?
the p-block
electronictransitions in triatomicmolecules of
do different molecular
geometries influence the
chemistry, how
21. Inthe context of inorganíc
can you provide specific examples?
spectroscopic behaviour of compounds, and
(OR)
chemistry of
techniques play in understanding the coordination interactions?
spectroscopic modes and ligand
22. What role do they used to determine bonding
transitionmetals, and how are
properties of
to study the electronicand magnetic
spectroscopic methods utilized compounds' reactivity?
23. How are insights do they offer into these
what
organometallic compounds, and and bonding of
appiied to investigate the coordination
is
how spectroscopyinforration their function?
24. Can you explain what it provides about
biomolecules, and
metal ions in

Calculate the best

UNIT V(12 marks) 4162, 8085 and
11779 cme-1.
vibrational freguencies of H2 are
25. The observed data.
7#)e based on this
value of oo, We,
observed
transitions have been
following ground state Frequency, MHz
26.For OCSe the
Transition 24514.67
Molecule 2>3 24410.58
16012C4Se 2’3 24030.58
16012C76Se 2’3 23880.18
1601C7Se 2’3
1601C80ge
for the
internuclear distances.
determine the best values
rigid rotor
Consider 0CSe to be a
2
B(sCT+)
)
 TUetURE H

CHEM-423
Ist SESSIONAL EXAMINATION
DEPARTMENT OF CHEMISTRY
PONDICHERRY UNIVERSITY
FM. 30 Time: 1.5 hr Date: 22.07.23
1 What would be the splitting pattern in the 'H NMR of CHDE 2
2 Write in increasing order of chemical shift values for the following protons (in bold). 2
sCoH, p-Cl-CoH-Cl, ColH_CO,H, CH,-CH-CH-CI, CH;CQ,CH, PhCH;
3 Consider the molecule CICH;CHFCH;CI
(i) How mnany chemically different types of protons are there?
(i)What would be the splitting patern of the CHF proton in principle? 2
4 Inthe 'H NMR spectrum of N-methyl-2,4.6-trinitroaniline there are two peaks in
the aromnatic region of the spectrum at low temperature but only one peak in that
region at high temperature-explain.
Write the following J values in an increasing order of coupling{co_tantandgive
2

the reag,.c
2JHD, Jn JHH 2
cnantiotonie diastereotopic and homotonic CH% (underlined and bÍld) protons in 3
Shw the CH).CO.CH).CO.CH3, and
CHBr.CH,CH3,
the following compounds. CH,CH2
CO;H.CH).CO;H and 3
element X has three naturally occurring isotopes, "X (30%), nX(40%), Draw the
An has a non-zero nuclear spin (| =
1/2).
(30%). Of these isotopes, "X write the
nX
spectrum of tetrahedral (CH3)4X, given that JK-H= 20Hz and
"H NMR
intensity ratio of the peaks. cunslants 3
approximate chemicals shift (in ppm), splitting patterns and coup!ing
8 Write the E-ÇHC=CHCCOCH;CH,.
(inHz) for the compound a 60 MHz3
four peaks of a doublet of triplets, collected in coupling
8 values of the and 7.36 ppm. Calculate the peaks
7.03, 7.07, 7.11, 7.28, 7.32
instrument, are of these six
coupling constant and the &values
constants. What would be the
a 300 MHz instrument?
if the datawere collected in
3
compound with molecular formula C11H402. The
10 Draw the structure for a 'H-NMR data.
compound shows the following (t, 3H)
7.1-7.2 (m, SH), 4.1 (t, 2H), 2.9(t, 2H), 2.1 (q, 2H), 1.0 and "C NMR spectra data 5
a molecular formula CiuH140. "H H
11 This compound has the
structure of the compound and assign the l3C and
the
are given below. Draw DEPT
peaks. Normal DEPT
Normal DEPT DEPT Carbon -135 -90
Carbon -135 -90 Positive Positive
129
14 ppm Positive No peak 133 Positive Positive
22 Negative No peak No peak No peak
137
26 Negative No peak No peak No peak
200
38 Negative No peak
Positive Positive 8Hz, 2H),
128
1H), 7.49 (m, 2lH), 2.96 (t, 8Hz, 2H), 1.44 (qn,
'H NMR: 7.90(m, 2H), 7.67 (m, 8Hz, 3H)
0.93 (t,
1.35 (sextet, 8Hz, 2H),
 Pondicherry University
School of Physical, Chernical and Applied Sciences
Department of Chemistry
Sessional Assessment - July 12, 2023
CHEM 421: Reaction Kinetics and Mechanism
M.Sc., Chemistry First Year

Max. Duration: 1.5 h Max. Marks: 30

Answer ALL questions

fast reaction and its significance. (4)

1. Describe stopped flow technique for studying
reaction follows LFER (5)
that Bronsted equation for acid-base
substituent and reaction constants? (3)
the important contributions of
3.What are
the reactions (4)
P4Which factors influence the nucleophilicityof
(4)
Lewis concept of acids and bases
5. Briefly discuss
product if the reactioinundergoes both thermodynamic
do you get same (3)
reactions?
and kinetic control
reaction is equal to the (3)
that the ratio of the rate constants of parallel
7. Prove with a suitable diagram.
ratio of the product yields
(4)
Principle with potentialenergy diagrams.
6. Describe Curtin-Hammett

Ew

-END clen
 Department of Chemistry, Pondicherry University
M.Sc. Internal Examination, July -2023
CHEM 421: Reaction Kinetics and Mechanism (UNIT-)
Max. Marks: 20 M
Time: hr
nos L

10 x 2 = 20 M
the following
Answer any ten questions from
2M
suitable examples.
Compare SN' and SN reactions with 2M
following reaction.
2. Write the major product of the
OTf 1. CsF

2. MeOH
SiMe3
2M.
following transformation.
reagerts for the
. dentif the svitable
NH2
NHCOCH NO,

2M

stereochemistry.
C with proper
4. Find out A, B and
PPh3 C
OH NaNg B
K,CO3 A H,0
ethyl
tBu "Br
reactions ofphenyl ethanoate and 2M
products formed from the
5 What are the major
HNO3/ H2SO4 in presence
of heat?
following
benzoate with step-wisesynthesis ofthe
explainthe 2M
benzene as the startingmaterial,
6. Paking -0-0R
compound.
Br

Br Br 2M
mechanism.
reactionwith a suitable
thefollowing R -O - o R
7/Predictthe productof

SO3
H,SO4
Ha8O4

bondel to CG,
 2M
following compounds from Benzene?
8. How would you make the
a) m-bromonitrobenzene
b) m-bromoacylbenzene
2M
transformation.
9/ Explain the mechanism involved in the following

H,0
iPrOH

Nucleophilic Substitution Reaction with suitable

10. Write a short note on Vicarious 2M
examples.
2M
11. Explain the E1CB-Elimination reaction with suitable examples.

stereochemistry wherever
12. W:ite the major product of the following reactions (Show 2M
necessary).

PhMgBr mCPBA
A) B)
H,SO4, H,0 H,0, HCIO4
 PONDICHERRY UNIVERSITY

Department of Chemistry
CHEM 424: Structure and bonding in coordination &organometallic compounds
of transition metals

SESSIONAL EXAMINATION II
Time: Two Hours Maximum Marks: 30

Answer Al the Questions

PART-A (5 x3=15 marks)

1. Predict the product for the following reactions and explain the structure of the products.
G CpXeNC,TPh{CAO)M:)} vith CF;SO;H
(i)CpMn(CO);THF reaction with CHN2
2. How will youprepare the following?
() [CpFe(CO)Me] from [CpFe(CO):] (i) [Cp:Ta(Me)2]* with
3. Predict the products and structures for the following reaction co
() 2eq. of [CpCo(CO)2] with light (i) [Mn(CO)s(CH,CHCH)] with light
4. Explain the nature of FMOs of FoCp2 and Sintcraction.
5. Predict the products for the following reactions and discuss about the structure of the products
(i) CpCo(CzH4)2 + 3MeCHCHMe (ii) Co(CO)8 with BuCP in THF at 25 °C
ilcos CHy -CH:
PART-B (15 marks)
Ch CH-C,
1. Write the biologically important bulk & trace metal ions and justify your answer. (2 marks)
condition. (2 marks)
2. Explain how the inhalation of large quantity of CO leads to fatal

3. Explain the formation of oxymyoglobin and oxyhemoglobin using equations

and oxygen binding curves. ((3 marks)

4. Compare and contrast the hemerythrin and hemocyanin interms of their

structural and functional aspects. (4 marks)

5. Explain the structural features of myoglobin and hemoglobin and illustrate the
oxygenation properties using Perutz mechanism. (4 marks)