Chemistry

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Subject Chemistry
Paper No and Title Paper 5: Organic Chemistry-II (Reaction Mechanism-I)
Module No and Title Module 1: Types of Organic Reactions
Module Tag CHE_P5_M1_e-Text
CHEMISTRY PAPER No. 5: Organic Chemistry-II

(Reaction Mechanism-1)
MODULE No. 1: Types of Organic Reactions
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TABLE OF CONTENTS
1. Learning Outcomes
2. Introduction
3. Types of Organic Reactions
3.1 Substitution Reactions
3.2 Addition Reactions
3.3 Elimination Reactions
3.4. Rearrangement Reactions
3.5 Oxidation and Reduction Reactions
4. Summary

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After studying this module, you shall be able to
• Know the various types of organic reactions

• Learn the difference between each type of reaction
• Identify the reaction types depending upon reactants and conditions
• Analyze organic reactions
2. Introduction
An organic reaction is a change in structure or functional group leading to formation of a new
substance. The compound undergoing a change in structure or functional group is called a
reactant or substrate. The knowledge of organic reactions helps in the synthesis of useful
chemical compounds such as polymers, dyes, drugs, perfumes, cosmetics, fertilizers, food
preservatives.
3. Types of Organic Reactions

The organic reactions can be generally classified as substitution, addition, elimination,
rearrangement, oxidation and reduction reactions.
Substitution
Reactions
Oxidation and
Reduction Reactions Addition Reactions
Organic
Reactions
Rearrangement Elimination
Reactions Reactions
Fig 1: Types of organic reactions

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3.1 Substitution Reactions

These reactions involve the displacement of an atom or a group by another atom or group.
Substitution Raeaction
RCH2CH2X Y- RCH2CH2Y X-
Substrate Attacking Reagent Product Leaving Group
It takes place at
a) sp3 hybridised carbon (alkane, haloalkane, alcohol)
b) sp2 hybridised carbon (benzene)
A substitution reaction can be nucleophilic, electrophilic or free radical substitution reaction.
Nucleophilic Substitution Reaction
Substitution
Reactions Electrophilic Substitution Reaction
Free Radical Substitution Reaction
Fig 2: Types of substitution reactions
3.1.1 Nucleophilic Substitution Reactions
Attack of nucleophile at a saturated carbon atom, bearing a substituent known as leaving group
results in a nucleophilic substitution reaction. The compound on which substitution takes place is
called the substrate and the group that is displaced from carbon is called leaving group.
The nucleophilic reaction may follow the following pathways:
(a) Substitution nucleophilic unimolecular mechanism (SN1)
Such reactions proceed in two steps via formation of a carbocation intermediate and the product
obtained is a racemic mixture. For example, the hydrolysis of tertiary halides follow SN1
pathway. The initiation step is ionization of substrate which is slow and rate determining step.
The second step is a rapid reaction between the intermediate carbocation and the nucleophile.
Rate = k [RX]

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(b) Substitution nucleophilic bimolecular mechanism (SN2)
Such reactions proceed in one step via a transition state and inversion of configuration. For
example, the hydrolysis of primary halides follow SN2 pathway. In this mechanism, there is
backside attack, the nucleophile approaches the substate from the position 180o away from the
leaving group. This is a one step process with no intermediate.
Rate = k [RX] [Nu]
(c) Substitution nucleophilic internal mechanism (SNi)
In the reaction of alcohol with thionyl chloride, displacement of hydroxyl group by chloride
proceeds via SNi mechanism. In this reaction the configuration is retained and it follows second
order kinetics. In SNi mechanism, part of the leaving group must be able to attack the substrate,
detaching itself from the rest of the leaving group in the process.
Rate = k [ROH] [SOCl2]

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(d) Aromatic nucleophilic substitution (SNAr)
In nucleophilic aromatic substitution a strong nucleophile replace a leaving group. The initiation
step is usually, but not always, rate-determining. In general, the attacking species forms a bond
with the substrate, giving an intermediate and then the leaving group departs.
3.1.2 Electrophilic Substitution Reactions
It involves substitution in the aromatic ring by an electrophile. In the first step the electrophile is
attacked by the π-electrons of the aromatic ring leading to the formation of a new carbon-
electrophile bond. It is followed by loss of a proton. In these reaction, electrophile first attack to
give an intermediate with positive charge, known as arenium ion and in the second step leaving
group departs. This is known as arenium ion mechanism.
Examples of electrophilic substitution reactions are:

(a) Nitration: It involves a nitronium ion (NO2) as an electrophile.
(b) Sulphonation: In this reaction sulphur trioxide (SO3) acts as an electrophile.
3.1.3 Free Radical Substitution Reactions

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Such reactions begin with the formation of a free radical which substitutes a group or atom
present in the reactant molecule. The reaction of methane with chlorine in the presence of light is
a free radical substitution reaction.
CH4 + Cl2 CH3Cl + HCl
The first step is initiation i.e free radical formation by homolytic cleavage of bonds. Second step
is chain propagation and finally chain termination step
Initiation
Initiation step may happen spontaneously or may be induced by heat or light depending on the
type of bond.
Cl2 2Cl
Chain Propagation
In this step, a molecule reacts with a free radical to generate a new radical.
CH4 + Cl CH3 + HCl
CH3 + Cl2 CH3Cl + Cl
Chain termination
This step is also known as destruction of free radicals. This step involves a combination of two
like or unlike radicals to form a new bond.
2Cl Cl2
CH3 + Cl CH3Cl
CH3 + CH3 CH3CH3
3.2 Addition Reactions
These reactions are characteristic of compounds containing multiple bonds. The alkene (=),
alkynes (≡), C=O, C≡N react by addition to multiple bond. Thus in addition reaction there is
increase in the number of groups attached to the substrate and decrease in its unsaturation.
Addition reactions are of four type namely electrophilic, nucleophilic, free radical and concerted.
The first three are the two-step processes, with initial attack by electrophile, nucleophile or a free

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radical. The second step consists of a combination of the resulting intermediate with a negative
species, a positive species or a neutral entity. In addition, attack at the two carbon atoms of the
double or triple bond is simultaneous.
Electrophilic Addition
Nucleophilic Addition
Addition Reactions
Free Radical Addition
Concerted Addition
Fig 3: Types of addition reactions
3.2.1 Electrophilic Addition Reactions
The first step is addition of electrophile by formation of σ bond through donation of π electrons to
the electrophile and carbocation is formed. The next step is reaction of the positively charged
intermediate (carbocation) with a species carrying lone pair or negative charge i.e nucleophiles.
This step is the same as the second step of the SN1 mechanism.
Examples of electrophilic addition reactions:
(a) Addition of bromine to alkenes: The addition reaction of bromine to alkenes proceeds via a
cyclic bromonium ion intermediate. This intermediate is similar to those encountered in the
neighbouring-group mechanism of nucleophilic substitution. This reaction is used as a colour test
to detect the presence of multiple bonds. The brown colour of bromine disappears when it is
added to a compound with double or triple bonds.

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(b) Addition of unsymmetrical reagents to unsymmetrical alkenes (Markownikoff rule): For

example in the reaction of propene with HBr, H+ acts as an electrophile which is added to the
carbon bearing double bond followed by attack of bromide ion (Br-).
3.2.2 Nucleophilic Addition Reactions
Such reactions are encountered in compounds containing polar functional groups (C=O, C≡N,
C=S). In the first step a nucleophile with its pair of electrons attacks the carbon atom of a double
or triple bond, forming a carbanion. It is followed by a second step in which this carbanion reacts
with a positive species.
When the olefin contains a good leaving group (as defined for nuclepohilic substitution),
substitution is a side reaction.( i.e. a nucleophilic substitution at a vinylic substrate).
Examples of nucleophilic addition reactions:
(a) Addition of HCN to carbonyl group: In this reaction cyanide ion (CN-) acts as a nucleophile
which attacks the carbon of carbonyl group, the carbon-oxygen double bond breaks followed by
capture of proton and a cyanohydrins is formed.
(b)Addition of alcohol to carbonyl compounds: Aldehydes or ketone react with one mole of
alcohol to form hemiacetal or hemiketal, respectively. Reaction with second mole of alcohol
gives acetal or ketal. In this reaction the alcohol with lone pair of electrons of oxygen atom acts
as a nucleophile

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(c) Nucleophilic addition to carbon-carbon double bond (Michael reaction): In Michael reaction
a nucleophile adds on to the β-carbon of an α,β-unsaturated system having electron withdrawing
group. HY added to substrate having groups such as CHO, COR, COOR, CONH2, CN,NO2,
SOR,SOOR etc. always give a product with Y- bonding with the carbon away from the Z group
and follows nucleophilic mechanism.
CH2=CH-CN + H-Y ---------à Y-CH2-CH2-CN
This 1,4- addition is called as cyanoethylation because Y is cyanoethylated.
3.2.3 Free Radical Addition Reactions
Free radicals add to an unsaturated molecule to give a new radical intermediate which further
reacts to give final product. The radical is generated by photolight or spontaneous dissociation.
Example of free radical addition reaction:
Addition of HBr to alkene in presence of peroxide (Anti-Markownikoff addition) is a type of free

radical addition reaction. The peroxide acts as radical initiator. This is a stereoselective free-
radical addition reaction.
3.2.4. Concerted Addition Reactions
Concerted addition reactions occur by simultaneous attack at both the carbons. The initial attack
is not at one carbon of the double bond, but both carbons are attacked simultaneously. Most of
these reactions involve four-membered transition state but in few cases, there is a five- or six-
membered transition state. In these cases, the addition to the double or triple bond must be syn.
The most important reaction of this type is Diels-Alder reaction.

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Example of concerted addition reaction:
Hydroboration of alkene is a concerted addition reaction. Here, the formation of C-H and C-B
bonds takes place at the same time of breaking of the B-H bond.
H H H
B H H H
B
H B
H H
Alkene Concerted transition state Product
3.3 Elimination Reactions
In these reactions two atoms or groups attached to the carbon atom/s of the substrate molecule are
eliminated. These are of three types α, β and γ eliminations.
α-elimination (or 1,1- elimination): The two groups are eliminated from same carbon, for
example formation of carbene or nitrene.
OH- -Cl-
CHCl3 CCl3- :CCl2
-H+
Carbene
β-elimination (or 1,2-elimination): This is the most common elimination reaction in which the
two groups are eliminated from adjacent carbons creating a multiple bond. In most β-
eliminations, the new bonds are c=c or c≡c. The β-eliminations include acid catalysed
dehydration of alcohols, Hofmann elimination, dehydrohalogenation.

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γ-elimination: A three membered ring is formed in this case.
The β-elimination reactions follow two pathways E1 and E2.
3.3.1 Unimolecular Elimination Mechanism (E1)
The E1 reaction needs no good base or nucleophile, it proceeds via formation of a carbocation. It
is a two-step reaction involving formation of a carbocation followed by loss of proton giving
more substituted alkene as major product. Here, formation of carbocation by ionization of
substrate is the rate determining step. The carbocation so formed rapidly loses a β proton to a
base, usually the solvent. E1 is analogous to SN1 mechanism. The second step differs in that the
solvent pulls a proton from the β carbon of a carbocation rather than attacking it at the positively
charged carbon, as in the SN1 process. In E1 reaction, the product should be completely non-
stereospecific, since the carbocation is free to adopt its most stable conformation before losing
proton.
3.3.2 Bimolecular Elimination Mechanism (E2)
In E2 mechanism a strong base abstracts proton from the substrate and the electron pair form π-
bond with departure of leaving group, all this occurs in one step. The two groups are eliminated
simultaneously. It occurs in one step thus follows second order kinetics i.e.first order in substrate
and first order in base. E2 is analogous to the SN2 mechanism and often competes with it.
Dehydrohalogenation of alkyl halides to alkene is a bimolecular elimination reaction.
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3.4. Rearrangement Reactions
Molecular rearrangements involve migration of an atom or a group from one atom to another in
the same molecule. The rearrangement reactions proceed via the formation of cation, anion or
radical. The 1,2-rearrangement, pericyclic reactions and metathesis occur via rearrangement. The
atom A is called Migration Origin and B is the Migration terminus. The migration of any
substituent from one atom to the atom adjacent to it is known as 1,2- shifts, but some are
over longer distances.
Examples of rearrangement reactions:
(a) Pinacol-Pinacolone rearrangement: Conversion of 2,3-dimethylbutan-2,3-diol into 2,2-

dimethylbutan-3-one.
(b) Beckmann rearrangement: Conversion of an oxime to amide is a rearrangement reaction. In

most Beckmann rearrangements, only the groups trans (usually called anti) to the hydroxyl group
migrates.
(c) Pericyclic Reactions: A pericyclic reaction involves concerted bond reorganisation and the
essential bonding changes within a cyclic array of the participating atomic centres. In these types
of reaction neither ions nor radicals are formed as intermediate and remain unaffected by polar
reagents. They take place either photochemically or thermally.

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3.5 Oxidation and Reduction Reactions
Organic reactions are classified as oxidation or reduction depending on whether the substrate is
oxidised or reduced. For this the functional groups are arranged in order of increasing oxidation
state as follows:
Oxidation state -4 (alkane)

Oxidation state -2 (alkene, alcohol, alkyl halide, amine)
Oxidation state 0 (alkyne, carbonyl, dihalides, diols)
Oxidation state +2 (carboxylic acid, amide, trihalide)
Oxidation state +4 (carbon dioxide, carbon tetrachloride)
Oxidation is the conversion of a functional group in a molecule from one category to a higher one
and reduction is the opposite. In oxidation gain of oxygen or/and loss of hydrogen takes place.
Reduction is opposite to that of oxidation as here loss of oxygen or gain of hydrogen takes place.
Also there is no oxidation without a concurrent reduction.
Oxidation reactions are classified depending on the type of bond change involved.
Examples of oxidation reactions:
Elimination of hydrogen.
(a) Aromatisation: Conversion of cyclohexane to benzene in the presence of a catalyst is a type of

oxidation reaction which proceeds via loss of hydrogen. The most frequently used reagents to
affect aromatization are hydrogenation catalysts such as Pt, Pd, Ni etc. quinines, elements S, Se
etc.
(b) Oxidation or dehydrogenation of alcohols to aldehydes and ketones. Conversion of alcohol to

carbonyl: A variety of reagents such as CrO3, pyridinium chlorochromate (PCC), pyridinium
dichromate (PDC), DMSO/oxalyl chloride, DMSO/DCC, copper chromite, are used for
oxidation of alcohols to aldehyde or ketone. Primary alcohols are converted to aldehydes and
secondary alcohols are converted to ketones in four main ways:
1). With strong oxidizing agents .

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2). By catalytic dehydrogenation.
3). With NBS and other chemoselective oxidising agents.
(c) Cleavage of carbon- carbon bonds i.e. Ozonolysis: Reaction of alkenes with ozone under
suitable conditions leads to fission of carbon-carbon double bond via formation of an
intermediate ozonide.
Examples of reduction reaction:
(a) Conversion of carbonyl to alcohol: When aldehydes or ketones are converted to alcohol the
hydrogen content is increased thus it is a reduction reaction. The transfer of hydride ion by
lithium hydride to carbonyl is such an example. There are two methods known for the conversion
of carbonyl to alcohol, these are Clemmensen reduction and the wolff kishner reduction.
(b) Meerwein–Ponndorf–Verley reduction: It occurs in the presence of isopropyl alcohol and

aluminum isopropoxide. The reaction is reversible in nature and the reaction reverse to it is
named as the Oppenauer oxidation.
(c) Clemensen Reduction: In the Clemensen reduction a carbonyl compound is reduced to alkane
using amalgamated zinc and hydrochloric acid. Ketones are reduced more often than aldehydes.

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(d) Conversion of carboxylic ester to alcohol: Lithium hydride often brings out reduction of
carboxylic ester by hydride transfer via formation of aldehyde in first step and further hydride
transfer to the aldehyde leads to formation of alcohol. This reaction is of wide scope and has been
used to reduce many esters. Other common reagents used are DIBAL, Lithium
triethylborohydride, BH3-SMe2 in refluxing THF. NaBH4 reduces phenolic esters especially those
containing EWGs.
(e) Conversion of nitro compounds to amine: Conversion of nitro group to amine is a reduction
reaction which involves loss of oxygen and gain of hydrogen.
Both aliphatic and aromatic nitro compounds can be reduced to amines, though the reaction has
been applied much more often to aromatic nitro compounds. The other common reagents are Zn,
Sn or/and acid, AlH3-AlCl3, TiCl3, Al-NiCl2-THF, formic acid and Pd-C, etc.
4. Summary
• Organic reactions are of various types.

• Organic reactions are classified as substitution, addition, elimination, rearrangement,
oxidation and reduction.
• These reactions differ mechanistically from each other and on the nature of attacking
reagents.

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Subject Chemistry
Paper No and Title Paper No. 5:Organic Chemistry-II
Module No and Title Module No. 2: Overview of different types of Organic

Reaction Mechanisms
Module Tag CHE_P5_M2
CHEMISTRY PAPER No. 5: REACTION MECHANISM

MODULE No. 2: Types of Organic Reaction Mechanisms
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TABLE OF CONTENTS
2. Introduction
3.Types of Reaction Mechanisms
3.1 Substitution Nucleophilic Unimolecular Mechanism (SN1)
3.2 Substitution Nucleophilic Bimolecular Mechanism (SN2)
3.3 Substitution Nucleophilic Internal Mechanism (SNi)
3.4 Aromatic Nucleophilic substitution mechanism (SNAr)
3.5 Substitution Radical Nucleophilic Unimolecular(SRN1)
3.6 Electrophilic Aromatic Substitution Mechanism (EAS)
3.7 Unimolecular Elimination Mechanism (E1)
3.8 Bimolecular Elimination Mechanism (E2)
3.9 Conjugate Base Elimination Mechanism (E1cb)
3.10 Elimination Internal Mechanism (Ei)
3.11 Free Radical Mechanism
3.12 Concerted Mechanism
4. Summary

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After studying this module, you shall be able to:
• Know how organic reactions proceed.

• Identify the different types of reaction mechanisms.
• Analyse the difference between each type of mechanism.
2. Introduction
Reaction Mechanism: Mechanism for any reaction is defined as collection of number of
processes that explains the overall reaction.
• This is the actual method of completion of reaction as it gives the number of broken
bonds and the number of steps involved.
• In a mechanism thepositions of all atoms (stereochemistry), role of solvent molecules and
the energy of thesystem is specified.
• It also helps in describing the reaction intermediate, activated complex and transition
state involved in the whole reaction.
• A mechanism accounts for all the reactants used, the function of a catalyst, all products
formed and their amount.
• From a mechanism the rate law can be deduced.
You are already familiar with some common terms frequently encountered while discussing any
reaction mechanism as given below:
Substrate:In most reactions of organic compounds, one or more covalent bonds are broken.For
most reactions, it is convenient to call one reactant the attacking reagent and the other the
substrate.
Nucleophile and Electrophile: Reagent having an electron pair is known as nucleophile and
the reaction is nucleophilic. A reagent that takes an electron pair is called an electrophile and the
reaction is electrophilic.
Leaving Group: In a reaction in which the substrate molecule becomes cleaved, part ofit (the
part not containing the carbon) is usually called the leaving group. A leaving group that carries
away an electron pair is called a nucleofuge. If itcomes away without the electron pair, it is called
an electrofuge.
Reaction intermediates: Intermediates are those chemical species which are short-lived and
unstable. They are neither reactant nor product. They are said to be temporary products or
reactants generally free radicals or ions.
Transition states: It is an unstable intermediate molecular state with an unusual number of bonds
and/or unstable geometry.
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Molecularity: It is defined as number of colliding molecular entities involved in a single reaction

step.
• Unimolecular reaction step involve only one molecular entity.
• Bimolecular reaction step involve two molecular entities.
• Termolecular reaction step involve three molecular entities.
3. Types of Reaction Mechanisms
Organic reactions proceeds via various mechanisms some common mechanisms are SN1,
SN2, SNi, SNAr (addition-elimination, elimination-addition, aryl cation), SRN1, EAS,
E1,E2,E1cb,Ei,free radical mechanism and concerted mechanism.
SN1
Concerted SN2
Free
Radical SNi
REACTION
Ei MECHANISMS SNAr
E1cb SRN1
E2 EAS
E1
Figure 1: Types of reaction mechanisms
3.1.Substitution Nucleophilic Unimolecular Mechanism (SN1)
The reaction between tert alkyl halides (eg. tert-butylbromide) and water followsSubstitution
NucleophilicUnimolecular Mechanism (SN1).Unimolecular means that only one molecule is
involved in the rate-determining step.
The mechanism of SN1 reaction is as follows:

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• SN1 reaction proceeds in two steps.

• Step 1 is formation of carbocation.
• Step 2 is capture of carbocation by nucleophile.
• Follow first order kinetics. Because, the rate of the reaction depends on the concentration
of only one reactant i.e. alkyl halide in this case, the reaction is a first-order reaction.
• Rate law is define as:
Rate = k [RX]
• Two stereoisomers are formed for an alkyl halide having asymmetric carbon.Oneof the
products has the same relative configuration at the asymmetric carbon as the reacting
alkyl halide while the other has inverted configuration..
• The order of reactivity for alkyl halides is 3o> 2o>1o>CH3X
• As reaction proceeds through formation of carbocation there is possibility of
rearrangement to form more stable carbocation.
• SN1 is favoured in polar protic solvent and in the presence of weak nucleophile.
3.2 Substitution Nucleophilic Bimolecular Mechanism (SN2)
The reaction of methyl bromide with hydroxide ion follows SN2 mechanism.When the transition
state is reached, the central carbon atom has gone from its initial sp3 hybridisation to a sp2 state
with an approximately perpendicular p orbital. There are two lobes of p-orbital, one overlaps with
the leaving group and the other with nucleophile. During transition state the three non-reacting
substituents and the central carbon are in a same plane. This inversion of configuration is called
Walden inversion.

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The mechanism of SN2 reaction is as follows:
• An alkyl halide having an asymmetric carbon results in the formation of only one
stereoisomer and the inversion of configuration takes place.
• Reactions following SN2 mechanism occur in one step via formation of a transition state.
• The rate of the nucleophilic substitution depends upon the concentration of reactant,
methyl bromide in this case,if the concentration of reactant doubles, the rate of the
nucleophilic substitution reaction also doubles.
• The rate of the reaction also depends on nucleophile concentration. This means that both
reactants are involved in the rate determining step.
Hence the rate law is:
Rate = k [RX] [Nu]
• Polar aprotic solvents favour SN2.
3.3 Substitution Nucleophilic Internal Mechanism (SNi)

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Replacement of OH of alcohols by Cl in the presence of SOCl2 proceeds via SNi mechanism.

It follow second order rate law. This reaction proceeds with the retention of configuration.
Rate = k [ROH] [SOCl2]
3.4 Aromatic Nucleophilic Substitution Mechanism (SNAr)
In aromatic nucleophilic substitution mechanism a strong nucleophile replaces aleaving group.

It can be through an addition-elimination, elimination-addition or aryl cation mechanism.
3.4.1 The SNAr Addition-Elimination Mechanism
Here substitution takes place at ipso position. Presence of strong electron withdrawing group at
ortho/para to leaving group favors addition-elimination mechanism. It uses one of the vacant π*
orbitals for bonding interaction with the nucleophile. This allows addition of nucleophile to the
aromatic ring without displacing any substituent. Net substitution occurs in second step by
elimination of leaving group.

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Example of reaction undergoing through addition-elimination mechanism: Reaction of para-nitro

fluoro benzene with sodium methoxide.
It is a two step mechanism and proceeds as shown:

(i) Slow step: Aromaticity of ring is lost in this step. Nucleophile attacks on bond between
carbon and halogen.
The intermediate formed is stabilised via resonance. Presence of electron withdrawing group at
ortho or para position provides extra stabilisation.
(ii) Fast step: Aromaticity of the ring is restored in this step. Intermediate formed in first step
looseshalide.

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3.4.2 Elimination-Addition Mechanism (BenzyneMechanism)
Elimination-addition mechanism involves a highly unstable intermediate called dehydrobenzene

or benzyne.
Example of elimination-addition mechanism: Reaction of chlorobenzene with soda amide in

liquid ammonia. If the aryl halide contains two ortho substituents, the reaction should not occur.
The mechanism of this reaction is shown below:

(i) First step is elimination of proton ortho to the substituent present and formation of benzyne.

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(ii) Attack of amide ion on the benzyne intermediate.
(iii) Abstraction of proton from ammonia.
3.4.2 Aryl Cation Mechanism
The aromatic aryl cation SN1 mechanism is encountered with diazonium salts. The reaction rate is
first order in diazonium salt and independent of the concentration of nucleophile.

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3.5 Substitution Radical Nucleophilic Unimolecular(SRN1)
This was discovered in 1970 by Bunnett and Kim where, SRN1 stands for substitution radical-
nucleophilic unimolecular as it is similar to aliphatic SN1 reaction.
SRN1 is a substitution reaction in which nucleophilic substitution on aromatic compound takes
place.
Where, X is a halide.
.
An example of this reaction type is the Sandmeyer reaction which involves synthesis of aryl
halides from aryl diazonium salts via SRN1 mechanism.
3.6 Electrophilic Aromatic Substitution Mechanism (EAS)
It involves attack of π-system on electrophile and the stabilization of benzenonium ion through
resonance and removal of proton by base.

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Examples of reactions undergoing EAS mechanism are nitration, sulphonation, halogenations,

Friedel and Craft reactions. Ions formed in this mechanism are known as Wheland intermediates,
σ complexes or arenium ions.
1. Generation of electrophile
2. Attack of electrophile on aromatic ring forming carbocation intermediate
3. Deprotonation
3.7Unimolecular Elimination Mechanism (E1)
First step of a Unimolecular Elimination Mechanism (E1) is the loss of leaving group and
formation of a carbocation which is a slow and rate limiting step. The overall elimination is
completed by rapid removal of proton from adjacent carbon by attack of base (B:) leading to
formation of a double bond between the two carbon atoms.
• Rate of elimination is dependent on the concentration of the substrate.

i.e., Rate = k [RX].

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• Reaction is independent of nucleophile.

• Reaction is first order.
• It is favoured by protic polar solvent.
• Rearrangement may take place.
• A strong base not required.
• A good leaving group is required, such as a halide or a tosylate.
• The mechanism goes through carbocation intermediate, therefore rearrangement can take
place.
Example of Unimolecular Elimination Mechanism (E1): Dehydrohalogenation of alkyl halide.
3.8Bimolecular Elimination Mechanism (E2)
In the Bimolecular Elimination Mechanism (E2), a base (B:) abstracts a proton from a carbon
adjacent to the carbon attached to the leaving group. The electron pair left on the carbon force the
leaving group to leave and create a double bond. All this occur simultaneously in this mechanism.
• E2 is a one step process. C-H and C-X bond breaking takes place simultaneously in one
step.
• Rate of elimination depend on concentration of substrate and base. It follows second
order kinetics.
Rate = k [RX] [B]

• High concentration and strong base favours E2.
• It requires aprotic solvent.
• In E2 1,2-elimination takes place.

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• A good leaving group is required, such as a halide or a tosylate.
Examples of Bimolecular Elimination Mechanism (E2):

(i) Acid catalysed dehydration of alcohols.
(ii) Hoffman degradation of quarternary ammonium hydroxides.
(iii) The base induced elimination of hydrogen halide from alkyl halide.
3.9 Conjugate Base Elimination Mechanism (E1cb)
In a Conjugate Base Elimination Mechanism (E1cb) the C-H bond breaks with formation of
carbanion as intermediate. Formation of carbanion is fast and loss of leaving group is slow and
rate limiting. The greatest likelihood of finding E1cb mechanism is in substrates that have a) poor
nucleofuge b)an acidic hydrogen.
Rate = k [RX] [B]
The E1 mechanism requires formation of a primary carbocation,whereas the E1cb proceeds via a
carbanion intermediate.
3.10 Elimination InternalMechanism (Ei)
In Elimination Internal mechanism (Ei), two vicinal substituents on an alkane framework leave
simultaneously in a single step and formation of alkene takes place in a syn elimination.
Examples of Ei mechanism:
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(a) The Burgess Reagent or methyl N-(triethylammoniumsulfonyl)carbamate is a dehydrating

reagent mild in nature. it involves the conversion of secondary and tertiary alcohol to alkenes in a
syn-elimination.
(b) The Cope reaction is an elimination reaction involved in the formation of 5-membered cyclic
(intramolecular) transition state. In this reaction, alkene and a hydroxylamine is formed.
3.11 Free Radical Mechanism
In radical mechanism hemolytic bond cleavage takes place. The free radicals are involved in
chain reaction which leads to chain propagation. The final step chain termination involves
combination of two radicals. Initiation may happen spontaneously or may be induced by heat or
light.
Initiation:
Propagation:

____________________________________________________________________________________________________
Termination:
Peroxides such as benzoyl peroxide,dialkyl, diaryl and acyl peroxides are common source of
radical initiators. The O-O bond in peroxides is weak and reaction generally occurs at low
temperatures. Some organic compounds with low-energy bonds, such as azo compounds are also
used. Molecules that are cleaved by light are most often chlorine, bromine and various ketones.
3.12 Concerted Mechanism
Concerted reaction mechanism occurs without any intermediate. The transition state involves
bond breaking and bond formation. Reorganization of electrons via cyclic transition structures is
the process of concerted pericyclic reactions.
Diels-Alder reaction between diene and dienophile is an example of concerted cycloaddition

reaction.

____________________________________________________________________________________________________
4. Summary
• Mechanism for any reaction is define as collection of number of processes that explains
the overall reaction.
• The different types of mechanism via which an organic reaction may proceed are:
o Substitution Nucleophilic Unimolecular Mechanism (SN1)
o Substitution Nucleophilic Bimolecular Mechanism (SN2)
o Substitution Nucleophilic Internal Mechanism (SNi)
o Aromatic Nucleophilic Substitution Mechanism (SNAr)
o Substitution Radical Nucleophilic Unimolecular(SRN1)
o Electrophilic Aromatic Substitution Mechanism (EAS)
o Unimolecular Elimination Mechanism (E1)
o Bimolecular Elimination Mechanism (E2)
o Conjugate Base Elimination Mechanism (E1cb)
o Elimination Internal Mechanism (Ei)
o Free Radical Mechanism
o Concerted Mechanism

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Chemical bonding and properties of “layered” quaternary antimonide oxide
Published on 06 September 2011. Downloaded by N-List College Programme on 1/25/2024 5:00:20 PM.
REOZnSb (RE = La, Ce, Pr, Nd)

Kai Guo,a,b Zhen-Yong Man,a Xiao-Jun Wang,†a Hao-Hong Chen,a Mei-Bo Tang,a Zhi-Jun Zhang,a Yuri Grinc
and Jing-Tai Zhao*a
Received 20th April 2011, Accepted 12th July 2011
DOI: 10.1039/c1dt10721f
An efficient route to construct a three-dimensional crystal structure is stacking of two-dimensional

building blocks (2D-BBs). The crystal structures of potential thermoelectric compounds REOZnSb
(RE = La, Ce, Pr, Nd) were virtually constructed from insulating [REO] and conducting [ZnSb] layers.
Further optimizations performed by means of first-principles calculations show that REOZnSb should
exhibit semimetal or narrow band-gap semiconductor behaviors, which is a prerequisite for high
thermoelectric efficiency. The analysis of the electron localizability indicator for LaOZnSb reveals
mostly covalent polar interactions between all four kinds of atoms. The electron density yields
completely balanced ionic-like electronic formula La1.7+ O1.2- Zn0.4+ Sb0.9- . Furthermore, the samples of
REOZnSb have been synthesized via solid-state reaction, and their crystal structures were confirmed by
powder X-ray diffraction. The differences in cell parameters between the theoretically optimized and
the experimental values are smaller than 2%. The temperature dependence of the magnetic
susceptibility shows that LaOZnSb is diamagnetic above 40 K, whereas CeOZnSb, PrOZnSb and
NdOZnSb are Curie–Weiss-type paramagnets. Electrical conductivity and Seebeck effect measurements
indicate that REOZnSb are p-type semiconductors. A considerably high Seebeck coefficient and low
thermal conductivity were obtained for pure LaOZnSb, but its low electrical conductivity leads to a
small ZT. The high adjustability of the crystal structure as well as properties by optimization of the
chemical composition in the compounds REOZnSb provide good prospects for achieving high
thermoelectric efficiency.
1. Introduction of ZrCuSiAs can be considered as a model system for such a

consideration.
Till now, the rational design of new inorganic compounds absorbs The tetragonal crystal structure of ZrCuSiAs is built of [ZrSi]
solid-state chemists and materials scientists. Thereby serendipity and [CuAs] layers stacked alternately along the c-axis. It has the
plays an important role to explore new materials in spite of symmetry of the space group P4/nmm and was first described by
much time consumed.1–3 Controlling the crystal structure and Johnson and Jeitschko as a “filled” PbFCl type.11,12 Because of their
microstructure of materials is a prerequisite in order to master interesting physical properties, the tetragonal layered materials
distinct chemical and physical properties in solids. Therefore, containing transition elements gained a remarkable renaissance in
considerable efforts have been devoted to this field and two recent years; we mention here MCu[Q1-x Q¢x ]F (M = Ba, Sr; Q, Q¢ =
main approaches were proposed: computer simulation of the S, Se, Te),13,14 REOCuCh (RE = trivalent rare-earth metals; Ch = S,
energy landscapes in chemical systems4,5 and construction of Se, and Te),15,16 and REOMPn (RE = rare-earth metals; M = Mn,
new compounds of building blocks by using the concept inter- Fe, Co, and Ni etc.; Pn = P, As, Sb) etc.17–22 The iron oxyarsenides
growth or structural series.6–10 The well-known crystal structure were first prepared in W. Jeitschko’s group;23 later Yoichi Kamihara
et al. found a transition from a normal to a superconducting state
a
at 26 K in iron-based layered superconductor La[O0.89 F0.11 ]FeAs
Key Laboratory of Transparent Opto-Functional Inorganic Materials of
Chinese Academy of Sciences, Shanghai Institute of Ceramics, 1295 Ding due to the strong interactions between the electrons confined in
Xi Road, Shanghai, 200050, PR China. E-mail: [email protected]; the FeAs layer.19 LaOCuS has an optical band gap of 3.1 eV and
Fax: +86-21-52413122; Tel: +86-21-52412073 exhibits p-type electrical conductivity because of the hybridization
b
Graduate School of Chinese Academy of Sciences, 19A Yu Quan Road, of Cu and S states.24 The layered oxyselenide La1-x Srx CuOSe was
Beijing, 100039, PR China
c
Max-Planck-Institut für Chemische Physik fester Stoffe, Nöthnitzer Str.
reported as a candidate for thermoelectric material.25
40, Dresden 01187, Germany It might be reasonable to suppose that the inter-layer
† Current address: Laboratory of Inorganic Chemistry, ETH Zürich, and/or intra-layer atomic interactions in the compounds with
Wolfgang-Pauli-Straße 10, CH-8093 Zürich, Switzerland. this unique structure have significant influence on the novel
This journal is © The Royal Society of Chemistry 2011 Dalton Trans., 2011, 40, 10007–10013 | 10007
View Article Online
properties. So, LaOCuS represents a nice model system with p- 2.2. Characterization
type semiconducting behavior, emerging from the wide-gap or
insulating properties of oxides and narrow-gap or semiconducting X-Ray powder diffraction (XRPD) data of the samples REOZnSb
properties of chalcogenides.23 Representatives of the compounds at ambient temperature were collected on a Rigaku D/Max-
with layered crystal structure of the CaAl2 Ge2 type26 also show 2200 PC diffractometer at 40 kV and 40 mA (Cu Ka1 radiation,
distinct functionality of the layers (in the case of [ZnSb]), as l = 1.54056 Å, 2q range from 10◦ to 100◦ with a step size
in high-efficiency thermoelectric materials Cax Yb1-x Zn2 Sb2 27 and of 0.02◦ ). The atomic parameters of ZrCuSiAs were taken as
starting values and the crystal structures of LaOZnSb were refined
EuZn2 Sb2 .28 The intra-layer atomic interactions in [ZnSb] play a

significant role in electronic transport and the total thermoelectric using WinCSD software36 (full-profile Rietveld refinement) with
properties can be tuned by altering the intra-layer interaction anisotropic atomic displacement parameters for La, Zn, Sb, and
as well as the layer’s interaction with the embedded in-between an isotropic displacement parameter for the O. Seebeck coefficient
cations. The electronic and the thermal transport properties and electrical conductivity measurements were done under an
can be adjusted as independent as possibly to achieve a high argon atmosphere using an ULVAC-RIKO ZEM-3 system on
thermoelectric figure of merit ZT (ZT = (a 2 s/k )T, where a, s, prism-shaped samples. The thermal conductivity was obtained
k , and T are the Seebeck coefficient, electrical conductivity, total from the thermal diffusivity and the specific heat measured by
thermal conductivity, and absolute temperature, respectively).29,30 the laser flash technique (LFA 447, Netzsch). Magnetization
A combination of insulating and conducting layers in the same measurements (field cooling) were performed with a physical
structure might open the possibility to tune the properties in an property measurement system (PPMS) at applied fields (H) up
anisotropic manner, i.e. maintaining good electronic transport to 5 T.
properties in the conducting layer while achieving low ther-
mal conductivity involving the insulating layer. This constitutes 2.3. Electronic structure calculations and analysis of chemical
the basic needs for development of potential thermoelectric bonding
materials.
The crystal structure,31–33 Sb Mössbauer effect,32,34 low- First-principles calculations of the band structure were performed
temperature electrical,33 optical34 and magnetic properties35 have using the Castep code, which utilizes pseudopotentials to describe
been already studied for selected compounds REOZnSb (RE = electron–ion interactions and represents electronic wave functions
La–Nd, Sm). However, taking into account the above con- by means of a plane-wave basis set.37 Generalized gradient
siderations, an understanding of the chemical bonding in the approximation was applied to model the exchange–correlation
sense of the intergrowth concept and its relationship to the energy as formulated by Perdew, Burke and Ernzerhof.38,39 The unit
thermoelectric properties may build a new strategy in design cell parameters and atomic positional parameters were optimized
of new thermoelectrics. In this report we present the chemical applying ultra-soft pseudopotentials with a cutoff energy of
bonding, crystal structure and thermoelectrically relevant prop- 600 eV. Monkhorst–Pack meshes of (6 ¥ 6 ¥ 3) were used for
erties of quaternary antimonide oxide REOZnSb (RE = La, Ce, the integration in the Brillouin zone. The following states are
Pr, Nd). treated as valence states: La (5s2 5p6 5d1 6s2 ), Ce (4f1 5s2 5p6 5d1 6s2 ) Pr
(4f3 5s2 5p6 6s2 ), Nd (4f3 5s2 5p6 5d1 6s2 ), O (2s2 2p4 ), Zn (3d10 4s2 ) and
Sb (5s2 5p3 ). The residual forces and energy convergence tolerance
2. Experimental section were smaller than 0.01 eV Å-1 and 1.0 ¥ 10-6 eV atom-1 at the end
2.1. Preparation of samples of calculations.
Analysis of chemical bonding was carried out for LaOZnSb
The compounds were synthesized via solid-state reactions. Rare using the TB-LMTO-ASA program package.40 The Barth–Hedin
earth metals (La, Ce, Pr, Nd, purity 99.9%), oxides (La2 O3 , exchange potential41 was employed for the LDA calculations.
CeO2 , Pr6 O11 , Nd2 O3 , purity 99.999%), Zn metal (purity 99.999%), The radial scalar-relativistic Dirac equation was solved to get
and Sb metal (purity 99.999%) were used as starting materials. the partial waves. Because the calculation within the atomic
Stoichiometric amounts of constituents (ratio of RE : O : Zn : Sb = sphere approximation (ASA) includes corrections for the neglect
1 : 1 : 1 : 1) were put in graphite crucibles in a N2 -filled glove box of interstitial regions and partial waves of higher order,42 an
(H2 O/O2 levels below 0.1 ppm), then the crucibles were sealed addition of empty spheres was not necessary. The following radii
in evacuated silica tubes and heated up to 1173 K for 3 days of the atomic spheres were applied for the calculations: r(La) =
with a rate of 2 K min-1 . In order to make the solid reaction 1.802 Å, r(Zn) = 1.653 Å, r(Sb) = 1.953 Å, r(O) = 1.149 Å. A
complete and increase the homogeneity of the products, the basis set containing La(6s, 5d, 4f), Zn(4s, 4p, 3d), Sb(5s, 5p) and
resulting products were ground to fine powders and pressed into O(2p) orbitals was employed for a self-consistent calculation with
pellets. The pellets were sintered at 1173 K in an evacuated quartz La(6p), Sb(5d, 4f) and O(3s, 3d) functions being downfolded. The
tube and maintained for 2 days for the second stage of the solid- electron localizability indicator (ELI, Υ )43 was evaluated in the
state reaction. The as-synthesized black-colored samples after ELI-D representation according to ref. 44 and 45 with an ELI-D
cooling down to room temperature were kept in a glove box to module within the TB–LMTO–ASA program package.40 ELI-D
prevent oxidation. The bulk material for measuring thermoelectric and electron density were analyzed using the program Basin46 with
properties was prepared using LaOZnSb powder by Spark Plasma consecutive integration of the electron density in basins, which
Sintering (Dr Sinter SPS 2040 setup manufactured by Sythex SPS, are bound by zero-flux surfaces in the ELI-D or electron density
Tokyo) at 903 K for 5 min under uniaxial pressure of 70 MPa in a gradient field with a procedure proposed by R. F. W. Bader for the
vacuum. electron density.47
10008 | Dalton Trans., 2011, 40, 10007–10013 This journal is © The Royal Society of Chemistry 2011
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3. Results and discussion agreement between the experimental and theoretically optimized
structural parameters allowed the use of the latter for the further
3.1. Construction and optimization of the crystal structures of analysis of the ground-state properties.
REOZnSb
Within the intergrowth concept, the crystal structures of 3.2. Electronic structure of REOZnSb compounds
REOZnSb can be described by stacking of [REO] layers from
Electronic structure and density of states (DOS) were calculated
REOCl and [ZnSb] layers from NaZnSb along the tetragonal c-
on the basis of relaxed structures, as shown in Fig. 2. On the basis
axis, as shown in Fig. 1. Zinc is surrounded by four antimony

of these calculations, semiconducting or semimetallic behavior was
atoms forming edge-sharing tetrahedrons [ZnSb4/4 ], which are
predicted for all four compounds REOZnSb, as is necessary for
interconnected to produce a [ZnSb] layer. Similarly, a [LaO] layer
an efficient thermoelectric material. It should be mentioned that
is formed by edge-sharing tetrahedrons [OLa4/4 ]. The [LaO] layer
the value of the band gap is usually underestimated due to the
is supposed to be insulating, while the [ZnSb] layer should serve
well-known DFT reason using GGA as the exchange–correlation
as a carrier conduction path. Assuming the best possible match
potential.51 Therefore, the experimental gap is expected to be larger
of the layers, the lattice parameter a0 can be determined as the
than the calculated one. Fig. 3 shows the total density of states and
average value of a(REOCl) and a(NaZnSb). In this way, the
partial density of states of LaOZnSb in the energy range between
following initial lattice parameters were obtained: a0 = 4.2781 Å for
-35 eV to 7 eV, where five ranges can be recognized. With the
LaOZnSb, a0 = 4.2633 Å for CeOZnSb, a0 = 4.2465 Å for PrOZnSb
energy below -30 eV, the DOS is dominated by La 6s states. The
and a0 = 4.2400 Å for NdOZnSb. Utilizing the parameters a0 and
bonding band from -20 eV to -14 eV is mainly formed by La
the interatomic distances from the database,48 approximate values
5p and O 2s states, indicating considerable covalent interactions
of the c0 parameters, atomic coordinates zRE and zSb were calculated
between La and O. Mainly Sb 5s and Zn 3d states are located in the
according to the following equations:2
range of -11 eV to -6 eV and may also hybridize. It is worth noting
1 2 1 2 1 2 that both of the valence and conduction band widths extend 6 eV.
c 0 = 2 × ( d RE
2
−O − a0 + d RE −Sb − a0 + d Zn −Sb − a0 )
2 2
(1)
4 2 4
1 2
z RE = d RE
2
−O − a0
(2)
4 c0
1 2
z Sb = 0.5 + d Zn
2
−Sb − a0
(3)
4 c0
Fig. 2 Band structures of REOZnSb: (a) RE = La; (b) RE = Ce; (c) RE =

Pr; (d) RE = Nd.
Fig. 1 The LaOZnSb crystal structure (middle) as a stacking of the [LaO]

layers from LaOCl (left) and [ZnSb] layers from NaZnSb (right).
All parameters of the geometrically predicted structures are

listed in Table 1. The cell parameters a0 and c0 decrease with
the decreasing ionic radii of the rare-earth elements. Optimiza-
tions of the crystal structures were carried out through first-
principles calculations and the energy convergence indicated
the thermodynamical stability of the compounds in agreement
with the experimental results. The optimized parameters and
experimentally obtained values are summarized in Table 1 too.
The differences between the optimized and experimentally found
lattice parameters are within 2%, which is within the usual range Fig. 3 Total electronic DOS of LaOZnSb with partial contributions of
by this kind of optimization of the crystal structures.49,50 Close selected states.
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Table 1 The geometrically deduced, theoretically optimized and experimental unit cell parameters of REOZnSbc
LaOZnSb CeOZnSb PrOZnSb NdOZnSb
a0 /Å Geometrically deduced 4.278 4.263 4.247 4.240

Optimized 4.263 4.190 4.146 4.170
Experimental 4.229(5)a 4.202(4)a 4.183(1)a 4.163(6)a
4.2267(6)32 4.1976(4)31 4.1763(4)31 4.159(1)32
Differencesb -0.78% 0.29% 0.87% -0.14%
c0 /Å Geometrically deduced 8.553 8.246 8.299 8.097

Optimized 9.750 9.530 9.598 9.594
Experimental 9.552(2)a 9.494(8)a 9.462(3)a 9.456(2)a
9.538(2)32 9.474(1)31 9.451(1)31 9.454(4)32
Differencesb -2.0% -0.38% -1.44% -1.46%
RE(1/4 1/4 z) z = Geometrically deduced 0.1229 0.1252 0.1262 0.1212
Optimized 0.1235 0.1217 0.1184 0.1135
Sb(3/4 3/4 z) z = Geometrically deduced 0.7056 0.7144 0.7142 0.7200
Optimized 0.6767 0.6852 0.6858 0.6853
a
This work b Differences are calculated as (a0 (Opt.) - a0 (Exp.))/a0 (Exp.) and (c0 (Opt.) - c0 (Exp.))/c0 (Exp.). c The coordinates of O and Zn are (xO =
xZn = 0.75, yO = yZn = 0.25, zO = 0, zZn = 0.5).
The valence band below the Fermi level is mainly composed of Sb zinc (Zn0.4+ ), and 55.3 electrons for lanthanum (La1.7+ ), yielding
5s, Sb 5p and Zn 4s, Zn 3p states. The conduction band above the the completely balanced electronic formula La1.7+ O1.2- Zn0.4+ Sb0.9- .
Fermi level is dominated by Zn 4s, Zn 3p, Sb 5p and La 5d states. QTAIM charges and the charge transfer are in agreement with the
Therefore, the transport behaviors of the compounds REOZnSb electronegativity relationships between the components: EN(La)
may be different since the diffuse Zn-4s orbitals slightly hybridize < EN(Zn) < EN(Sb) < EN(O). The absolute values of the atomic
with the 5d- and 4f-orbitals of the rare earth element and thus the charges are smaller than those expected from the usual oxidation
energy is altered.52 states (+3 for La, -2 for O, +2 for Zn and -3 for Sb). This indicates
reduced ionicity and partial covalency of the atomic interactions
3.3. Chemical bonding in compounds REOZnSb in the crystal structure.
The bonding situation was analyzed in detail by means of
The chemical bonding pattern in LaOZnSb was further evaluated the electron localizability indicator in the ELI-D representation
by the analysis of the electron localizability indicator in combi- (Fig. 5). In the case of lanthanum, the sixth shell is completely
nation with the electron density. The evaluation of the electron absent. These electrons are transferred to the neighboring atoms.
density according to the QTAIM method of Bader47 yielded an Charge transfer causes ionic interaction of the lanthanum with
atomic basin for each atom. The shapes of the basins for La, its environment. In addition, the distribution of ELI-D in the
Zn, Sb and O are shown in Fig. 4. Integration of the electron penultimate (fifth) shell is strongly deviating from the spherical
density within the atomic basins gives 9.2 electrons for oxygen one, which is characteristic for the non-interacting atoms. This
(O1.2- ), 50.9 electrons for antimony (Sb0.9- ), 29.6 electrons for deviation is quantified by the structuring index e (the difference
Fig. 4 The shape of the QTAIM atomic volumes in LaOZnSb. The Fig. 5 Electron localizability indicator in LaOZnSb. Structuring of the
according charges are 9.2 e- for oxygen (O1.2- ), 50.9 e- for antimony outer shells of Sb and O as well as the penultimate (fifth) shell for La
(Sb0.9- ), 29.6 e- for zinc (Zn 0.4+ ), and 55.3 e- for lanthanum (La1.7+ ), yielding reveals their participation in the bonding. The structuring of the fourth
completely balanced formula La1.7+ O1.2- Zn0.4+ Sb0.9- . shell of Zn is only weakly recognizable.
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between the highest ELI-D value in the examined shell and Table 2 Experimental atomic coordinates and displacement parameters
the ELI-D value at which the localization domain is without a (pm2 ) for LaOZnSb. U eq is defined as one third of the trace of the
orthogonalized U ij tensor. U 12 = U 13 = U 23 = 0
‘hole’).53 For lanthanum it is 0.122, which is remarkably large for
an RE cation. Formation of ‘holes’ in the penultimate shell of Atom W. site x y z U 11 = U 22 U 33 U eq
lanthanum in the direction of the neighboring oxygen atoms and
a deformation of the second shell of oxygen is a signature of the La 2c 1/4 1/4 0.12050(8) 60(3) 82(4) 67(2)
Zn 2b 3/4 1/4 1/2 120(5) 131(9) 124(4)
(polar) covalent bonds between them. These bonds are mainly Sb 2c 1/4 1/4 0.68011(8) 84(3) 99(4) 89(2)
contributing to the formation of the [LaO] layers. O 2a 3/4 1/4 0 70(20)a

The formation of the [ZnSb] layers is less pronounced from a
Isotropic displacement parameters for O.
the point of view of chemical bonding. The most interesting is
the interaction between the zinc and the antimony: there are no
dedicated maxima on the Zn–Sb lines, which are usually expected Table 3 Interatomic distances (pm) for LaOZnSb
for a covalent interaction caused by a small electronegativity
La 4 O 240.79(4) Sb 4 Zn 272.59(5)
difference. Only in the structuring of the valence shell of Sb the
4 Sb 354.58(6) 4 La 354.58(6)
covalent character of this interaction may be recognized. At the Zn 4 Sb 272.59(5) O 4 La 240.79(4)
same time, a local enhancement of the ELI values is observed in the
third shell of zinc, toward lanthanum, indicating also a significant
refined from the XRD patterns are summarized in Table 1 and
covalent (polar) interaction. In addition, the valence shell of
are in agreement with the theoretical results with the differences
antimony (fifth) is also strongly structured. Here, already local
smaller than 2%. The X-ray powder pattern for LaOZnSb is shown
maxima are formed close to the lines to the neighboring oxygen
in Fig. 7. The parameters a0 = 4.23079(1) Å and c0 = 9.54560(6) Å
and lanthanum atoms from the neighboring [LaO] layer revealing
are obtained by the Rietveld technique. The atomic positional and
the (polar) covalent inter-layer interaction. Antimony behaves here
displacement parameters were refined and are listed in Tables 2
as an electron donor toward oxygen and an acceptor toward the
and 3. Furthermore, the distances between [REO] and [ZnSb] are
lanthanum atoms. Thus, analysis of the atomic interactions does
all larger than 1.84 Å ((zRE - zSb ) ¥ c0 ) obtained from optimization
not reveal clear separation between the [LaO] and [ZnSb] layers
results. Thus, it is expected that this natural ‘superlattice’ may
from the point of view of chemical bonding. This should have
scatter phonons, thus reducing the thermal conductivity.
consequences on the bonding-relevant transport properties, i.e.
reducing the thermal transport.
3.4. Syntheses, crystal structure and materials morphology of

REOZnSb
The X-ray diffraction patterns of as-synthesized REOZnSb sam-

ples are shown in Fig. 6. They match very well the simulated
pattern of optimized structures, indicating that the samples
are composed mainly of one phase, and only traces of ZnSb
as impurity were detected. The patterns were indexed with a
tetragonal lattice (space group P4/nmm). With the atomic radii
decreasing (from La to Nd), the diffraction peaks shift to the
higher angles systematically. The unit cell parameters indexed and
Fig. 7 Rietveld refinement result for LaOZnSb. The continuous profile

and dots represent the calculated XRD intensity and experimental data,
respectively. The bottom profile is the difference between the experimental
and calculated intensities (Rwp = 8.18%, RB = 4.97%).
3.5. Physical properties of REOZnSb
The temperature dependence of the molar magnetic susceptibility

of polycrystalline samples REOZnSb is presented in Fig. 8. The
measurements reveal diamagnetism above 40 K for LaOZnSb. In
contrary, CeOZnSb, PrOZnSb and NdOZnSb are paramagnetic.
The temperature dependencies follow the Curie–Weiss law c(T) =
C/(T - q), where c is the molar magnetic susceptibility, C =
N A meff 2 /3k B is the Curie constant, and q is the Weiss temperature.
Fig. 6 Calculated X-ray diffraction pattern for the optimized model of the A linear fit of the inverse magnetic susceptibility as a function
crystal structure of LaOZnSb in comparison with experimental patterns of the temperature is employed (Fig. 8(b)), yielding effective
of REOZnSb compounds prepared by solid-state reactions. Reflections of paramagnetic moments m of 2.44 mB , 3.41 mB and 3.21 mB
the impurity phase ZnSb are marked. characteristic for the trivalent Ce (4f1 ), Pr (4f2 ) and Nd (4f3 )
Published on 06 September 2011. Downloaded by N-List College Programme on 1/25/2024 5:00:20 PM. View Article Online
Fig. 8 Magnetic susceptibility vs. temperature for LaOZnSb (a) and the
inverse magnetic susceptibility vs. temperature for CeOZnSb, PrOZnSb
and NdOZnSb (b). Data are collected in a field-cooling mode (H = 5 T).
ions, respectively (cf. theoretical values of the magnetic moments

mCe3+ = 2.54 mB , mPr3+ = 3.5 mB and mNd3+ = 3.5 mB ).
The temperature dependencies of the electrical conductivity and
Seebeck coefficient for LaOZnSb are shown in Fig. 9 (a) and (b).
With increasing temperature from 300 K to 665 K, the Seebeck
coefficient decreases from +206 mV K-1 to +160 mV K-1 , suggesting
a p-type conductivity. On the contrary, the electrical conductivity
monotonously increases from 6.0 ¥ 102 S m-1 to 1.9 ¥ 103 S m-1 ,
originated from more carriers excited at elevated temperature.
During the activation temperature of intrinsic carriers, the band
gap can be extracted from the carrier activation-dominated elec-
trical conductivity. As can be seen in Fig. 9 (a) insert, a ln(s/s 0 )–
1000/T plot was carried out to obtain the band gap. On the basis of
the slope coefficient calculated from the curve, the value of 0.3 eV
was determined. The room-temperature electrical conductivity
of LaOZnSb is larger than that of the isomorphic compounds
LaOZnP and LaOZnAs because of a smaller value of the band
gap (LaOZnP ª 1.7 eV; LaOZnAs ª 1.5 eV).54,55 In comparison
with another related compound La0.95 Sr0.05 CuOSe24 and FeSb2 ,56 Fig. 9 Temperature dependences of (a) electrical conductivity, (b) See-
LaOZnSb exhibits high electrical conductivity and a large Seebeck beck coefficient, (c) thermal conductivity and (d) thermoelectric figure of
coefficient above room-temperature, thus large power factors merit ZT for LaOZnSb.
(a 2 s). The thermal conductivities are all well below 1.5 W m-1
K-1 (Fig. 9 (c)), revealing a targeted low thermal conductivity. 4. Conclusions
Thus, the experimental results are in good agreement with the
above discussed theoretical calculations. The thermoelectric figure The structural models of the compounds REOZnSb (RE = La, Ce,
of merit ZT for LaOZnSb increases with increasing temperature Pr, Nd, ZrCuSiAs-type) obtained from the intergrowth concept
from 0.005 at 311 K to 0.032 at 665 K and may reach higher above were optimized by first-principle calculations. Analysis of chemical
665 K from the trend of the curve. Although a considerably high bonding in the optimized LaOZnSb revealed polar covalent
Seebeck coefficient and low thermal conductivity were obtained interaction between La and O, and between Zn and Sb. In addition,
for LaOZnSb, its low electrical conductivity leads to a small ZT. inter-layer covalent interactions between Sb and La and O are
View Article Online
detected. Band structure and electronic DOS calculations on the 21 H. H. Wen, Adv. Mater., 2008, 20, 3764.
optimized structure models predicted narrow-gap semiconducting 22 B. I. Zimmer, W. Jeitschko, J. H. Albering, R. Glaum and M. Reehuis,
J. Alloys Compd., 1995, 229, 238.
behavior for all four compounds REOZnSb (RE = La, Ce, Pr, 23 P. Quebe, L. J. Terbüchte and W. Jeitschko, J. Alloys Compd., 2000, 302,
Nd). The predicted crystal structures and physical behaviors were 70.
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Paper No and Title Paper 5: Organic Chemistry-II (Reaction Mechanism-I)

Module No and Title Module 1: Types of Organic Reactions

Module Tag CHE_P5_M1_e-Text

CHEMISTRY PAPER No. 5: Organic Chemistry-II

CHEMISTRY PAPER No. 5: Organic Chemistry-II

• Know the various types of organic reactions

3. Types of Organic Reactions

Fig 1: Types of organic reactions

CHEMISTRY PAPER No. 5: Organic Chemistry-II

3.1 Substitution Reactions

A substitution reaction can be nucleophilic, electrophilic or free radical substitution reaction.

Nucleophilic Substitution Reaction

Free Radical Substitution Reaction

Fig 2: Types of substitution reactions

3.1.1 Nucleophilic Substitution Reactions

The nucleophilic reaction may follow the following pathways:

(a) Substitution nucleophilic unimolecular mechanism (SN1)

CHEMISTRY PAPER No. 5: Organic Chemistry-II

(b) Substitution nucleophilic bimolecular mechanism (SN2)

Rate = k [RX] [Nu]

(c) Substitution nucleophilic internal mechanism (SNi)

Rate = k [ROH] [SOCl2]

CHEMISTRY PAPER No. 5: Organic Chemistry-II

(d) Aromatic nucleophilic substitution (SNAr)

3.1.2 Electrophilic Substitution Reactions

Examples of electrophilic substitution reactions are:

(b) Sulphonation: In this reaction sulphur trioxide (SO3) acts as an electrophile.

3.1.3 Free Radical Substitution Reactions

CHEMISTRY PAPER No. 5: Organic Chemistry-II

CH4 + Cl2 CH3Cl + HCl

CH4 + Cl CH3 + HCl

CH3 + Cl2 CH3Cl + Cl

CH3 + CH3 CH3CH3

3.2 Addition Reactions

CHEMISTRY PAPER No. 5: Organic Chemistry-II

Fig 3: Types of addition reactions

3.2.1 Electrophilic Addition Reactions

Examples of electrophilic addition reactions:

CHEMISTRY PAPER No. 5: Organic Chemistry-II

(b) Addition of unsymmetrical reagents to unsymmetrical alkenes (Markownikoff rule): For

3.2.2 Nucleophilic Addition Reactions

Examples of nucleophilic addition reactions:

CHEMISTRY PAPER No. 5: Organic Chemistry-II

CH2=CH-CN + H-Y ---------à Y-CH2-CH2-CN

This 1,4- addition is called as cyanoethylation because Y is cyanoethylated.

3.2.3 Free Radical Addition Reactions

Example of free radical addition reaction:

Addition of HBr to alkene in presence of peroxide (Anti-Markownikoff addition) is a type of free

3.2.4. Concerted Addition Reactions

CHEMISTRY PAPER No. 5: Organic Chemistry-II

Example of concerted addition reaction:

Alkene Concerted transition state Product

3.3 Elimination Reactions

CHEMISTRY PAPER No. 5: Organic Chemistry-II

γ-elimination: A three membered ring is formed in this case.

The β-elimination reactions follow two pathways E1 and E2.

3.3.1 Unimolecular Elimination Mechanism (E1)

3.3.2 Bimolecular Elimination Mechanism (E2)

3.4. Rearrangement Reactions