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1. Consider 18 electron rule as a guide and determine the value of n in the following
complexes
solution
2. A metal complex having the empirical formula FeC9H7O3Cl, has one ligand as a
substituted cyclopentadienyl group. It is an ionic compound and has poor
solubility in hydrocarbon solvents. The compound gives a white precipitate on
treatment with AgNO3 solution. Assuming that it obeys the 18 electron rule,
suggest its structure.
solution
CH3
Cl
Fe CO
OC
CO
3. In a carbonyl complex with linear CO-M-CO group, how will νCO change when
a) one CO is replaced by Et3N b) a positive charge is put on the complex c) a
negative charge is placed on the complex.
Solution
νco will change as follows,
a) Since Et3N is a sigma donor only and not an acceptor, the back donation
from M to the CO’s will increase and hence υco will decrease. b) less back
bonding because of positive charge and hence υco increases c) back
bonding increases because of negative charge, and hence υco decreases.
Mn2(CO)10 + 2 Na 2 NaMn(CO)5
H H H
H
Fluorene H H
H H
H H
solution
PF6
Fe H H
Fe
A B
6. Which among the following compounds will not undergo oxidative addition of
methyl iodide ? Give reasons
(a) Ir(PPh3)2(CO)Cl (b) [RhI2(CO)2]- (c) η5-Cp2Ti(Me)Cl
Solution
(c) As titanium is already in its highest oxidation state of +4 and therefore no
d electrons present for further oxidation
7. Mark against each statement the appropriate type of reaction or reactions from
the list (oxidative addition, reductive elimination, migratory insertion and β-H
transfer)
(a) cis orientation of the participating ligands is a must.
(b) This reaction does not occur for d0 metal complexes.
(c) This reaction is enthalpy favoured and entropy prohibited.
(d) A vacant coordination site on the metal centre is a prerequisite.
(e) The more electron rich the metal centre, the more facile is the reaction.
(f) There is an increase in the electron count of the metal complex by two units
during this reaction.
Solution
(a) Red elimination and migratory insertion
(b) Oxidative addition
(c) Migratory insertion
(d) Oxidative addition and β-H transfer
(e) Oxidative addition
(f) Oxidative addition and β-H transfer
H
Ph2 Ph2
OC P Et3Si P
Ir + excess Et3Si-H Ir + HBr + Et3Si-SiEt3
Br P H P
Ph2 Ph2
CO
Solution
H
Ph2 Ph2
Ph2 oxidative reductive
Et3Si P Et Si P
OC P addition elimination 3
Ir Ir
Ir + Et3Si-H -HBr
Br P OC P
Br P Ph2 16e Ph2
Ph2 CO
16e 18e
oxidative
+ Et3Si-H addition
H H
Ph2 oxidative Ph2 Ph2
Et3Si P reductive
addition H P elimination
Et3Si P
Ir Ir Ir
+ Et3Si-H -Et3Si-SiEt3
H P OC P Et3Si P
Ph2 Ph2 Ph2
18 e CO 16e 18e CO
3. Trimetallic complexes of phosphido bridges are well known. Assuming that the
18e rule is followed, postulate the structure of [Mn(μ-PH2)(CO)4]3.
H2 K
A A B excess C2H4 B
Na/Hg H
H - KC5H5
H
H
CO
C - 1/2 C5H5 dimer C
OC CO
CO
9. Benzene, on heating with D2 and the precatalyst η5- Cp2TaH3, gets converted to
monodeuterobenzene and finally to hexadeutero benzene. The reaction involves
only oxidative additions (both C6H5-H and D-D) and reductive eliminations.
Suggest a mechanism for the formation of monodeutero benzene (C6H5-D) from
benzene.
( hint: the active form of the catalyst is a 16 electron species )
10. The given metal-alkene intermediate is unstable and undergoes a rearrangement
resulting in the formation of three different arylalkene complexes of the general
formula Pd(PPh3)2(Br)(H)(η2 -alkene). Predict the structures of the three
arylalkene palladium complexes.
Br PPh3
Pd
Ph3P CH
C
H2C H2
CH3
11. Wilkinsons catalyst, RhCl(PPh3)3 catalyzes the reaction of trimethylsilyl hydride
[(CH3)3Si-H] with ethylene to give ethyltrimethylsilane[(CH3)3Si-CH2CH3]. Show
steps involved and mark the electron count and type of reaction at each step.