Geometrical Isomerism Notes | EduRev

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Geometrical Isomerism:
The isomerism which arises due to restricted (frozen) rotation about a bond in a molecule is known as geometrical or cis-trans isomerism. The rotation either about a double bond or about a single bond incorporated in a ring is restricted. Also, there may be restricted rotation about a single bond due to steric hindrance, e.g., as in biphenyls.  Compounds having restricted rotation about a bond exhibit geometrical isomerism if they are suitable substituted.

Geometrical (eis-trans) isomerism is exhibited by a variety of compounds which may be classified as follows:

  • Compounds containing a double bond C = C, C = N, N ≡ N.
  • Compounds containing cyclic structure; homocyclic, heterocyclic and fused ring, ring systems.
  • Compounds having restricted rotation about a single bond due to steric hindrance; some biphenyls,

No ostereoisomerism can result from triply bonded tetravalent or trivalent atoms because such systems display cylindrical symmetry.


CONDITIONS FOR GEOMETRICAL ISOMERISM
A compound will show geometrical isomerism if it fulfils the following two conditions:

  • There should be restricted (frozen) rotation about a bond in the molecule.
  • Both substitutents on each carbon about which rotation is frozen (restricted ) should be different.

Example
Alkenes
Geometrical Isomerism Notes | EduRev
Cycloalkanes
Geometrical Isomerism Notes | EduRevThe above compounds will not show geometrical isomerism.

Geometrical Isomerism Notes | EduRevThe above compounds will show geometrical isomerism
Geometrical Isomerism Notes | EduRevThe above compounds will not show geometrical isomerism.

NOMENCLATURE
The compounds of the type abC = Cab can exist in the following two forms due to frozen rotation about carbon-carbon double bond.
Geometrical Isomerism Notes | EduRev
This isomer in which similar groups are placed on the same side is called cis and the isomer in which the similar groups are on opposite sides is called trams.


Cis-trans nomenclature can be used only in those compounds in which type of substituents on both doubly carbons are two or three.

Example
Geometrical Isomerism Notes | EduRevCis-trans nomenclature cannot be used in those compounds where type of substituents resent on both doubly bonded carbons are four (or all four substitents are different).
Geometrical Isomerism Notes | EduRev


NUMBER OF GEOMETRICAL ISOMERS IN POLYNENS

Case -1: When two ends of chain are different Number of geometrical isomers = 2nd (where, n = number of double bonds)
Case -2: When two ends of chain are same
(a)  n = even, number of geometrical isomers =Geometrical Isomerism Notes | EduRev
(b)  n = odd, number of geometrical isomers =Geometrical Isomerism Notes | EduRev

E AND Z SYSTEM OF NOMENCLATURE
When four different atoms or groups are attached to the carbon atoms of a double bond, the E, Z system of nomenclature is used. The system is based on CIP rule.
Geometrical Isomerism Notes | EduRevExample:
Geometrical Isomerism Notes | EduRev
Geometrical Isomerism Notes | EduRev
Geometrical Isomerism Notes | EduRev
Geometrical Isomerism Notes | EduRev
Rules for assigning:-

  • Higher priority is assigned to the atoms of higher atomeic number.
    Example: order of priority: 53I >35Br >17CI >9F >8O >1H
  • For isotopes, the isotope of higher mass number is given higher priority
    Example: Order of priority:3T >2D >1H
  • In the groups, the order of priority is based on the higher atomic number of the first atom of the group.
    Example: order of priority:
    Geometrical Isomerism Notes | EduRev
  • When the order of priority of groups cannot be decided on the first atom than the second atom or the subsequent atoms in the groups are considered.
    Example: order of priority:
    Geometrical Isomerism Notes | EduRev
  • If an atoms is doubly or triply bonded to another atom, the priority system treats it as if it were singly bonded to those atoms.
    Example:
    Geometrical Isomerism Notes | EduRev

GEOMETRICAL ISOMERISM IN NITROGEN COMPOUNDS

Geometriacl isomerism due to >C = N- bond.

The important class of compounds exhibiting geometrical isomerism due to > C = N – bond are: (i) Oximes (ii) Nitrones (iii) Hydrazones and semicarbazones. But the most common compound is 

oxime.

Oximes: In aldoxime, when hydrogen and  hydroxyl groups are on the same side, the isomer is known as syn (analogous to cis) and when these groups are on the opposite sides, the isomer is known as anti (anglogous to trans)
Geometrical Isomerism Notes | EduRevIn ketoximes the prefixes syn and anti indicate as to which groups of ketoxime is syn or anti to hydroxyl group example:
Geometrical Isomerism Notes | EduRev
This compound will be named as:
(i) Syn-ethyl methyl ketoxime ⇒ HO and C2Hare syn.
(ii) Anti-methyl ethyl ketoxime ⇒ HO and CH3 are anti.
Geometrical Isomerism Notes | EduRev
Geometrical isomerism in cycloalkanes: Disubstituted cycloalkanes show geometrical isomerism.
Geometrical Isomerism Notes | EduRev
DEFINITION
Isomers which possess the same molecular and structural formula but differ in the arrangement of atoms or groups in space due to restricted rotation are known as geometrical isomers and the phenomenon is known as geometrical isomerism.

Conditions of geometrical Isomerism 
(i) Geometrical isomerism arises due to the presence of a double bond or a ring structure
(i.e.Geometrical Isomerism Notes | EduRev,- N = N - or ring structure).
Due to the rigidity of double bond or the ring structure to rotate at the room temperature the molecules exist in two or more orientations. This rigidity to rotation is described as restricted rotation l hindered rotation l no rotation at each dou.
(ii) Different groups should be attached bly bonded atom.
For example:
Geometrical Isomerism Notes | EduRevare identical but not geometrical isomers.
Example:
(A)Geometrical Isomerism Notes | EduRev
(Restricted Rotation)
(B)Geometrical Isomerism Notes | EduRev
(Restricted Rotation)
On the other hand, following types of compounds can exist as geometrical isomers :
Geometrical Isomerism Notes | EduRev
Examples of Geometrical isomers:
(i) AlongGeometrical Isomerism Notes | EduRevbond
Geometrical Isomerism Notes | EduRevand
Geometrical Isomerism Notes | EduRevand
Geometrical Isomerism Notes | EduRev
(ii) AlongGeometrical Isomerism Notes | EduRev
Geometrical Isomerism Notes | EduRevand
Geometrical Isomerism Notes | EduRevand
Geometrical Isomerism Notes | EduRevand
Geometrical Isomerism Notes | EduRev
Geometrical Isomerism Notes | EduRevand
Geometrical Isomerism Notes | EduRev
(iii) Along - N = N - bond
Geometrical Isomerism Notes | EduRevand
Geometrical Isomerism Notes | EduRev
Geometrical Isomerism Notes | EduRev
(iv) Along s bond of cycloalkane
Geometrical Isomerism Notes | EduRev
Geometrical Isomerism Notes | EduRevand
Geometrical Isomerism Notes | EduRev
Geometrical Isomerism Notes | EduRevand
Geometrical Isomerism Notes | EduRevand
Geometrical Isomerism Notes | EduRev
(v) AlongGeometrical Isomerism Notes | EduRevin ring structures:
Usually in cycloalkenes double bond has its configuration. Their trans isomers do not exist due to large angle strain. But if the ring is large enough a trans stereoisomer is also possible. The smallest trans cycloalkene that is stable enough to be isolated & stored is transcyclooctene.
Geometrical Isomerism Notes | EduRev
Configurational nomenclature in geometrical Isomerism:

ConfigurationCriteriaRemarks
cis / transSimilarity of groupsIf the two similar groups are on same side of restricted bond the configuration is cis otherwise trans.
E/ZSeniority of groupsIf the two senior groups are on same side of restricted bond the configuration is Z (Z = zusammen = together) otherwise E (E = entgegen = opposite).


Sequence rules: (Cahn - Ingold - Prelog sequence rules) For deciding the seniority of groups, following rules are applied :
Ruel 1: The group with the first atom having higher atomic number is senior. According to this rule the seniority of atom is : I > Br > Cl > S > F > O > N > C > H
Rule 2: The higher mass isotope is senior.

Thus
(A) - T > - D > - H.
(B) - C14H3 > - C12H3 
Rule 3: If the first atom of group is identical then second atom is observed for seniority. e.g.
(A) - CH2Cl > - CH2OH > - CH2NH2 > - CH2CH3 > - CH3
(B)Geometrical Isomerism Notes | EduRev
Rule 4: Groups containing double or triple bonds are assigned seniority as if both atoms were duplicated or triplicated that > C = Y as if it wereGeometrical Isomerism Notes | EduRev& - C º Y as if it wereGeometrical Isomerism Notes | EduRev
e.g. for deciding seniority among - C º CH, - CH = CH2, their hypothetical equivalents are compared.
Geometrical Isomerism Notes | EduRev

Rule 5: Bond pair gets priority over lone pair.

Rule 6: Z > E & R > S.


Number of Geometrical Isomers: Number of geometrical isomers can be found by calculating the number of stereocentres in the compound. (stereocentre is defined as an atom or bond bearing groups of such nature that an interchange of any two groups will produce a stereoisomer).

Physical Properties of Geometrical Isomers

Physical propertiesGeometrical Isomerism Notes | EduRevRemarks
Dipole momentI > IIcis-isomer has resultant of dipoles while in trans isomer dipole moments cancel out.
Boiling pointI > IIMolecules having higher dipole moment have higher boiling point due to larger intermoleculer force of attraction.
Solubility (in H2O)I > IIMore polar molecules are more soluble in H2O.
Melting pointII > IMore symmetric isomers have higher melting points due to better packing in crystalline lattice & trans isomers are more symmetric than cis.
StabilityII > IThe molecule having more Vander Waals' strain are less stable. In cis isomer the bulky groups are closer they have larger vander Waals' strain.


Table

Physical propertiesGeometrical Isomerism Notes | EduRev
Dipole momentI > II
Boiling pointI > II
Solubility (in H2O)I > II
Melting pointI > II
StabilityI > II
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