Total Pages-12

PG-IV-Sem
Chem-401

PG FOURTH SEMESTER EXAMINATION, 2022

CHEMISTRY

(Inorganic Chemistry - IV)

Paper-401
Full Marks: 80

Time:3 hours

Answer all questions

Marks have been mentioned in the right-hand corner

1.
1. Answer all the questions (multiple choice
questions): Ix12

( Which of the following is labile ?

(a) Rh
(6) TP*
(c) Rus

(a) Cr*

(Turn Over)
 is INCORRECT about the
(i) Which statement
mechanisms of electron transfer 2

(a) Electron transfer may occur by an inner

or outer-sphere mechanism depending
on the system

(6) Long range electron-transfers such as in

cytochromes are most likely to occur
by outer-sphere mechanisms
c) Marcus-Hush theory
applies to inner
-sphere mechanisms
(d) In an
inner-sphere mechanism, electron
transfer between two metal centers
involves a bridging
ligand
(iii) Which statement is correct ?
(a) A dissociative
mechanism is a 2-step
mechanism with the
departing in the second leaving group
step
(b) An associative mechanism is a
mechanism; the intermediate 2-step
a lower
coordination number than thehas
complex starting
PG-IV-SemChem-401
(Continued)
 (3)

c) In a dissociative interchange mecha

bond over
nism, breaking dominates
bond formation
(d) In an associative interchange mecha
nism, the entering group associates with
the substrate after the
leaving group has
departed
(iv) Which metal centre does not obey the
18-clectron rule?
(a) Fe in Feln-CH,COMe),
(b) Co in Co,(CO),
(c)Ruin [RulnC,Me),f"
(d) V in V
(CO),
(A Fischer-type carbene contains all but one
of the following, which is the odd one
out ?
(a) An M-Cbond
(b) A nucleophilic carbene centre
(c)A low oxidation state metal centre
attached to the metal-bound C atom
(d) A heteroatom (e.g. O)

PG-IV-SemChem-401
(Turn Over )
 (4)

(vi) Matchthe ligand to the number of electrons

available for bonding toa low oxidation
state metal. Which pair is incorrect?
(a) NO;2
(6) PPh, 2
(c) CH=CHCH=CH,;2or 4
(4) PhPCH,CH,PPh,; 2 or 4

(vi) In the
hydrogenation of alkenes using
Wilkinson's catalyst, the active
catalyst is
RhCI(PPh), (or RhCl(PPh,), (solvent)).
The first step in the catalytic cycle is:
(a) Alkene coordination
b) Oxidative addition of H,
(c) Loss of PPh,
(d) Loss of Cl

(viii) In a metal alkyl compound, which

R group could a-bonded
undergo B-hydrogen elimi-
nation?
(a) Et

PG-IV-SemCbem-401
(Continued )
 5)

(b) CH,Ph
(e) CHCMe
(d) Me

(ix) The reaction:

Mn(CO) Me +CO > Mn(CO)(COMe)
is an example of:

(a) A ligand addition

hA B-elimination
(c) An oxidative addition
An alkyl migration
(x) Which of the following electromagnetic
radiations used in ESR?

(ay Microwaves
(b) Radio waves
(c) IR
X-rays
(xi) Which of the following will NOT show
electron spin resonance (ESR) ?

(a) Free radicals

(Turn Over)
PG-IV-Sem/Chem-401
 6) 7

(b) Diamagnetic materials the non

(c) Paramagnetic materials
( )Discuss the complementary and
complementary two-clectron transfer reac
(d) Transition metals tions giving suitable examples.

UNIT II
(ri) For free electron, the value of g would be

(a) 1.0013 () Count the electrons in the following com-

(6) 3.0023 pounds and indicate the electron count per

metal unit.
() 6.0165s
4) 2.0023 CO cO

2.2. Answer any eight questions selecting two oc

questions from each Unit (Short answer type CO

question within two to three sentences): 2 x8

(ii) For an 18 electron complex ion,

UNIT-I
[Fe(CN),(NO)]2 what is the expected
M-N-O angle? Why ?
(9 What is annationreaction ? Give one suitable
example. (iii) What are stable alkyls ? Give an example.

i) Explain why the transfer of electron from UNIT- II

TFe(CN)/[Fe(CN),] is faster than () Write the mechanism involved in the olefin
[Co(NHJPJC%(NH,),J* ? metathesis.

PG-IV-SemChem-401 (Continued) PG-IV-Sem/Chem-401

(Tun Over)
 8) .9 .)

ii) What is hydrosilation reaction ? (ii) Discuss the mechanism of acid catalyzed
hydrolysis reaction.
(iii) What do you mean by isomerization reac-
tion?
UNIT -II
UNIT-IV (i) How do you synthesis ferrocene? Write any
Calculate moment for two reactions of ferrocene.
( spin only magnetic
CoC) ion.
(iiy Account for the following trend in IR
(i) What do you mean by Zero field splitting? v (NO) = 1515 cm
ICHCN),NO)*
(ii) Calculate the total number of hyperfine =
v (NO) 1725 cm
[Ma(CN),(NO)*
splitting's in [Cu(NH),]where Cu, I =3/2 =
Fe(CN),(NO)* v (NO) 1939 cm-
andN, I =1.
3. Answer any eight questions selecting two (iii) Write a short note on Fullerene complexes.
questions from each Unit (Short answer type
UNIT-II
question within 75 words) 3x8

UNIT-I () Write a short note on carbonylation reaction.

() Discuss the nature of the inner-sphere elec- (i) Discuss the factors which favours the easy
tron transfer mechanism. reductive elimination.

(i) What do you know about the labile and inert (iii)Indicate how 1-butene and 2-butene are
complexes? formed in the following reactions by writing

PG-IV-SemCn 401 (Continued) PG-IV-SemChem-401

(Turn Over)
 10 11

suitable mechanism. Show that no alkanes Or

a

are produced in this roaction.

(i) What is base hydrolysis ? Discuss the
possible mechanism. Why base hydrolysis
-butene is faster than acid hydrolysis ?

2-butene
P UNIT- II
Ph

() What are
carbenes ? Differentiate between
UNIT- IV
Fischer and Schrock carbene.

()Discussspin-orbit coupling. Or

(i) What is Magnetic susceptibility ? How does (i) Discuss the synthesis, structure and bonding
it vary with temperature ? of Zeise's salt.

( i )Writea short note on Kramer's degeneracy. UNIT-III

(1) What do you mean by hydroformylation?

4.
4. Answer any one question from each Unit. (Long Discuss the mechanism for hydroformyla-
answer type question within 300 words) : 7x4 tion.

UNIT- II Or
() What is trans effect? Discuss its theories (i) What do you mean by oxidative addition ?
and applications. What are the different types of oxidative

PG-IV-SemChem401 PG-IV-Sem/Chem-401 (Turn Over)

(Continued)
 12

addition reactions ? Explain the mechanism

of anyone with suitable example.

UNIT-IV
What do you understand about hyperfine
splitting ? Discuss the reasons for hyperfine
splitting.
Or

(i) Discuss Lande interval rule.