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1 | 4805-4808 | 7
Optical isomers
(d and l) of cis-
[PtCl2(en)2]2+
Fig 5 5
The facial (fac) and
meridional (mer)
isomers of
[Co(NH3)3(NO2)3]
Example 5 4
Example 5 |
1 | 4806-4809 | 5 5
The facial (fac) and
meridional (mer)
isomers of
[Co(NH3)3(NO2)3]
Example 5 4
Example 5 4
Example 5 |
1 | 4807-4810 | 5
The facial (fac) and
meridional (mer)
isomers of
[Co(NH3)3(NO2)3]
Example 5 4
Example 5 4
Example 5 4
Example 5 |
1 | 4808-4811 | 4
Example 5 4
Example 5 4
Example 5 4
Example 5 |
1 | 4809-4812 | 4
Example 5 4
Example 5 4
Example 5 4
Rationalised 2023-24
127
Coordination Compounds
Linkage isomerism arises in a coordination compound containing
ambidentate ligand |
1 | 4810-4813 | 4
Example 5 4
Example 5 4
Rationalised 2023-24
127
Coordination Compounds
Linkage isomerism arises in a coordination compound containing
ambidentate ligand A simple example is provided by complexes
containing the thiocyanate ligand, NCS
–, which may bind through the
nitrogen to give M–NCS or through sulphur to give M–SCN |
1 | 4811-4814 | 4
Example 5 4
Rationalised 2023-24
127
Coordination Compounds
Linkage isomerism arises in a coordination compound containing
ambidentate ligand A simple example is provided by complexes
containing the thiocyanate ligand, NCS
–, which may bind through the
nitrogen to give M–NCS or through sulphur to give M–SCN Jørgensen
discovered such behaviour in the complex [Co(NH3)5(NO2)]Cl2, which is
obtained as the red form, in which the nitrite ligand is bound through
oxygen (–ONO), and as the yellow form, in which the nitrite ligand is
bound through nitrogen (–NO2) |
1 | 4812-4815 | 4
Rationalised 2023-24
127
Coordination Compounds
Linkage isomerism arises in a coordination compound containing
ambidentate ligand A simple example is provided by complexes
containing the thiocyanate ligand, NCS
–, which may bind through the
nitrogen to give M–NCS or through sulphur to give M–SCN Jørgensen
discovered such behaviour in the complex [Co(NH3)5(NO2)]Cl2, which is
obtained as the red form, in which the nitrite ligand is bound through
oxygen (–ONO), and as the yellow form, in which the nitrite ligand is
bound through nitrogen (–NO2) This type of isomerism arises from the interchange of ligands between
cationic and anionic entities of different metal ions present in a complex |
1 | 4813-4816 | A simple example is provided by complexes
containing the thiocyanate ligand, NCS
–, which may bind through the
nitrogen to give M–NCS or through sulphur to give M–SCN Jørgensen
discovered such behaviour in the complex [Co(NH3)5(NO2)]Cl2, which is
obtained as the red form, in which the nitrite ligand is bound through
oxygen (–ONO), and as the yellow form, in which the nitrite ligand is
bound through nitrogen (–NO2) This type of isomerism arises from the interchange of ligands between
cationic and anionic entities of different metal ions present in a complex An example is provided by [Co(NH3)6][Cr(CN)6], in which the NH3 ligands
are bound to Co
3+ and the CN
– ligands to Cr
3+ |
1 | 4814-4817 | Jørgensen
discovered such behaviour in the complex [Co(NH3)5(NO2)]Cl2, which is
obtained as the red form, in which the nitrite ligand is bound through
oxygen (–ONO), and as the yellow form, in which the nitrite ligand is
bound through nitrogen (–NO2) This type of isomerism arises from the interchange of ligands between
cationic and anionic entities of different metal ions present in a complex An example is provided by [Co(NH3)6][Cr(CN)6], in which the NH3 ligands
are bound to Co
3+ and the CN
– ligands to Cr
3+ In its coordination
isomer [Cr(NH3)6][Co(CN)6], the NH3 ligands are bound to Cr
3+ and the
CN
– ligands to Co
3+ |
1 | 4815-4818 | This type of isomerism arises from the interchange of ligands between
cationic and anionic entities of different metal ions present in a complex An example is provided by [Co(NH3)6][Cr(CN)6], in which the NH3 ligands
are bound to Co
3+ and the CN
– ligands to Cr
3+ In its coordination
isomer [Cr(NH3)6][Co(CN)6], the NH3 ligands are bound to Cr
3+ and the
CN
– ligands to Co
3+ This form of isomerism arises when the counter ion in a complex salt
is itself a potential ligand and can displace a ligand which can then
become the counter ion |
1 | 4816-4819 | An example is provided by [Co(NH3)6][Cr(CN)6], in which the NH3 ligands
are bound to Co
3+ and the CN
– ligands to Cr
3+ In its coordination
isomer [Cr(NH3)6][Co(CN)6], the NH3 ligands are bound to Cr
3+ and the
CN
– ligands to Co
3+ This form of isomerism arises when the counter ion in a complex salt
is itself a potential ligand and can displace a ligand which can then
become the counter ion An example is provided by the ionisation
isomers [Co(NH3)5(SO4)]Br and [Co(NH3)5Br]SO4 |
1 | 4817-4820 | In its coordination
isomer [Cr(NH3)6][Co(CN)6], the NH3 ligands are bound to Cr
3+ and the
CN
– ligands to Co
3+ This form of isomerism arises when the counter ion in a complex salt
is itself a potential ligand and can displace a ligand which can then
become the counter ion An example is provided by the ionisation
isomers [Co(NH3)5(SO4)]Br and [Co(NH3)5Br]SO4 5 |
1 | 4818-4821 | This form of isomerism arises when the counter ion in a complex salt
is itself a potential ligand and can displace a ligand which can then
become the counter ion An example is provided by the ionisation
isomers [Co(NH3)5(SO4)]Br and [Co(NH3)5Br]SO4 5 4 |
1 | 4819-4822 | An example is provided by the ionisation
isomers [Co(NH3)5(SO4)]Br and [Co(NH3)5Br]SO4 5 4 3 Linkage
Isomerism
5 |
1 | 4820-4823 | 5 4 3 Linkage
Isomerism
5 4 |
1 | 4821-4824 | 4 3 Linkage
Isomerism
5 4 4 Coordination
Isomerism
5 |
1 | 4822-4825 | 3 Linkage
Isomerism
5 4 4 Coordination
Isomerism
5 4 |
1 | 4823-4826 | 4 4 Coordination
Isomerism
5 4 5 Ionisation
Isomerism
Out of the following two coordination entities which is chiral
(optically active) |
1 | 4824-4827 | 4 Coordination
Isomerism
5 4 5 Ionisation
Isomerism
Out of the following two coordination entities which is chiral
(optically active) (a) cis-[CrCl2(ox)2]
3–
(b) trans-[CrCl2(ox)2]
3–
The two entities are represented as
Draw structures of geometrical isomers of [Fe(NH3)2(CN)4]
–
Solution
Solution
Solution
Solution
Solution
Out of the two, (a) cis - [CrCl2(ox)2]
3- is chiral (optically active) |
1 | 4825-4828 | 4 5 Ionisation
Isomerism
Out of the following two coordination entities which is chiral
(optically active) (a) cis-[CrCl2(ox)2]
3–
(b) trans-[CrCl2(ox)2]
3–
The two entities are represented as
Draw structures of geometrical isomers of [Fe(NH3)2(CN)4]
–
Solution
Solution
Solution
Solution
Solution
Out of the two, (a) cis - [CrCl2(ox)2]
3- is chiral (optically active) Example 5 |
1 | 4826-4829 | 5 Ionisation
Isomerism
Out of the following two coordination entities which is chiral
(optically active) (a) cis-[CrCl2(ox)2]
3–
(b) trans-[CrCl2(ox)2]
3–
The two entities are represented as
Draw structures of geometrical isomers of [Fe(NH3)2(CN)4]
–
Solution
Solution
Solution
Solution
Solution
Out of the two, (a) cis - [CrCl2(ox)2]
3- is chiral (optically active) Example 5 5
Example 5 |
1 | 4827-4830 | (a) cis-[CrCl2(ox)2]
3–
(b) trans-[CrCl2(ox)2]
3–
The two entities are represented as
Draw structures of geometrical isomers of [Fe(NH3)2(CN)4]
–
Solution
Solution
Solution
Solution
Solution
Out of the two, (a) cis - [CrCl2(ox)2]
3- is chiral (optically active) Example 5 5
Example 5 5
Example 5 |
1 | 4828-4831 | Example 5 5
Example 5 5
Example 5 5
Example 5 |
1 | 4829-4832 | 5
Example 5 5
Example 5 5
Example 5 5
Example 5 |
1 | 4830-4833 | 5
Example 5 5
Example 5 5
Example 5 5
Solution
Solution
Solution
Solution
Solution
Example 5 |
1 | 4831-4834 | 5
Example 5 5
Example 5 5
Solution
Solution
Solution
Solution
Solution
Example 5 6
Example 5 |
1 | 4832-4835 | 5
Example 5 5
Solution
Solution
Solution
Solution
Solution
Example 5 6
Example 5 6
Example 5 |
1 | 4833-4836 | 5
Solution
Solution
Solution
Solution
Solution
Example 5 6
Example 5 6
Example 5 6
Example 5 |
1 | 4834-4837 | 6
Example 5 6
Example 5 6
Example 5 6
Example 5 |
1 | 4835-4838 | 6
Example 5 6
Example 5 6
Example 5 6
Rationalised 2023-24
128
Chemistry
This form of isomerism is known as ‘hydrate isomerism’ in case where
water is involved as a solvent |
1 | 4836-4839 | 6
Example 5 6
Example 5 6
Rationalised 2023-24
128
Chemistry
This form of isomerism is known as ‘hydrate isomerism’ in case where
water is involved as a solvent This is similar to ionisation isomerism |
1 | 4837-4840 | 6
Example 5 6
Rationalised 2023-24
128
Chemistry
This form of isomerism is known as ‘hydrate isomerism’ in case where
water is involved as a solvent This is similar to ionisation isomerism Solvate isomers differ by whether or not a solvent molecule is directly
bonded to the metal ion or merely present as free solvent moleculesin
the crystal lattice |
1 | 4838-4841 | 6
Rationalised 2023-24
128
Chemistry
This form of isomerism is known as ‘hydrate isomerism’ in case where
water is involved as a solvent This is similar to ionisation isomerism Solvate isomers differ by whether or not a solvent molecule is directly
bonded to the metal ion or merely present as free solvent moleculesin
the crystal lattice An example is provided by the aqua
complex [Cr(H2O)6]Cl3 (violet) and its solvate isomer [Cr(H2O)5Cl]Cl2 |
1 | 4839-4842 | This is similar to ionisation isomerism Solvate isomers differ by whether or not a solvent molecule is directly
bonded to the metal ion or merely present as free solvent moleculesin
the crystal lattice An example is provided by the aqua
complex [Cr(H2O)6]Cl3 (violet) and its solvate isomer [Cr(H2O)5Cl]Cl2 H2O
(grey-green) |
1 | 4840-4843 | Solvate isomers differ by whether or not a solvent molecule is directly
bonded to the metal ion or merely present as free solvent moleculesin
the crystal lattice An example is provided by the aqua
complex [Cr(H2O)6]Cl3 (violet) and its solvate isomer [Cr(H2O)5Cl]Cl2 H2O
(grey-green) 5 |
1 | 4841-4844 | An example is provided by the aqua
complex [Cr(H2O)6]Cl3 (violet) and its solvate isomer [Cr(H2O)5Cl]Cl2 H2O
(grey-green) 5 4 |
1 | 4842-4845 | H2O
(grey-green) 5 4 6 Solvate
Isomerism
Werner was the first to describe the bonding features in coordination
compounds |
1 | 4843-4846 | 5 4 6 Solvate
Isomerism
Werner was the first to describe the bonding features in coordination
compounds But his theory could not answer basic questions like:
(i) Why only certain elements possess the remarkable property of
forming coordination compounds |
1 | 4844-4847 | 4 6 Solvate
Isomerism
Werner was the first to describe the bonding features in coordination
compounds But his theory could not answer basic questions like:
(i) Why only certain elements possess the remarkable property of
forming coordination compounds (ii) Why the bonds in coordination compounds have directional
properties |
1 | 4845-4848 | 6 Solvate
Isomerism
Werner was the first to describe the bonding features in coordination
compounds But his theory could not answer basic questions like:
(i) Why only certain elements possess the remarkable property of
forming coordination compounds (ii) Why the bonds in coordination compounds have directional
properties (iii) Why coordination compounds have characteristic magnetic and
optical properties |
1 | 4846-4849 | But his theory could not answer basic questions like:
(i) Why only certain elements possess the remarkable property of
forming coordination compounds (ii) Why the bonds in coordination compounds have directional
properties (iii) Why coordination compounds have characteristic magnetic and
optical properties Many approaches have been put forth to explain the nature of
bonding in coordination compounds viz |
1 | 4847-4850 | (ii) Why the bonds in coordination compounds have directional
properties (iii) Why coordination compounds have characteristic magnetic and
optical properties Many approaches have been put forth to explain the nature of
bonding in coordination compounds viz Valence Bond Theory (VBT),
Crystal Field Theory (CFT), Ligand Field Theory (LFT) and Molecular
Orbital Theory (MOT) |
1 | 4848-4851 | (iii) Why coordination compounds have characteristic magnetic and
optical properties Many approaches have been put forth to explain the nature of
bonding in coordination compounds viz Valence Bond Theory (VBT),
Crystal Field Theory (CFT), Ligand Field Theory (LFT) and Molecular
Orbital Theory (MOT) We shall focus our attention on elementary
treatment of the application of VBT and CFT to coordination compounds |
1 | 4849-4852 | Many approaches have been put forth to explain the nature of
bonding in coordination compounds viz Valence Bond Theory (VBT),
Crystal Field Theory (CFT), Ligand Field Theory (LFT) and Molecular
Orbital Theory (MOT) We shall focus our attention on elementary
treatment of the application of VBT and CFT to coordination compounds According to this theory, the metal atom or ion under the influence of
ligands can use its (n-1)d, ns, np or ns, np, nd orbitals for hybridisation
to yield a set of equivalent orbitals of definite geometry such as octahedral,
tetrahedral, square planar and so on (Table 5 |
1 | 4850-4853 | Valence Bond Theory (VBT),
Crystal Field Theory (CFT), Ligand Field Theory (LFT) and Molecular
Orbital Theory (MOT) We shall focus our attention on elementary
treatment of the application of VBT and CFT to coordination compounds According to this theory, the metal atom or ion under the influence of
ligands can use its (n-1)d, ns, np or ns, np, nd orbitals for hybridisation
to yield a set of equivalent orbitals of definite geometry such as octahedral,
tetrahedral, square planar and so on (Table 5 2) |
1 | 4851-4854 | We shall focus our attention on elementary
treatment of the application of VBT and CFT to coordination compounds According to this theory, the metal atom or ion under the influence of
ligands can use its (n-1)d, ns, np or ns, np, nd orbitals for hybridisation
to yield a set of equivalent orbitals of definite geometry such as octahedral,
tetrahedral, square planar and so on (Table 5 2) These hybridised orbitals
are allowed to overlap with ligand orbitals that can donate electron pairs
for bonding |
1 | 4852-4855 | According to this theory, the metal atom or ion under the influence of
ligands can use its (n-1)d, ns, np or ns, np, nd orbitals for hybridisation
to yield a set of equivalent orbitals of definite geometry such as octahedral,
tetrahedral, square planar and so on (Table 5 2) These hybridised orbitals
are allowed to overlap with ligand orbitals that can donate electron pairs
for bonding This is illustrated by the following examples |
1 | 4853-4856 | 2) These hybridised orbitals
are allowed to overlap with ligand orbitals that can donate electron pairs
for bonding This is illustrated by the following examples 5 |
1 | 4854-4857 | These hybridised orbitals
are allowed to overlap with ligand orbitals that can donate electron pairs
for bonding This is illustrated by the following examples 5 5
5 |
1 | 4855-4858 | This is illustrated by the following examples 5 5
5 5
5 |
1 | 4856-4859 | 5 5
5 5
5 5
5 |
1 | 4857-4860 | 5
5 5
5 5
5 5
5 |
1 | 4858-4861 | 5
5 5
5 5
5 5 Bonding in
Bonding in
Bonding in
Bonding in
Bonding in
Coordination
Coordination
Coordination
Coordination
Coordination
Compounds
Compounds
Compounds
Compounds
Compounds
5 |
1 | 4859-4862 | 5
5 5
5 5 Bonding in
Bonding in
Bonding in
Bonding in
Bonding in
Coordination
Coordination
Coordination
Coordination
Coordination
Compounds
Compounds
Compounds
Compounds
Compounds
5 5 |
1 | 4860-4863 | 5
5 5 Bonding in
Bonding in
Bonding in
Bonding in
Bonding in
Coordination
Coordination
Coordination
Coordination
Coordination
Compounds
Compounds
Compounds
Compounds
Compounds
5 5 1 Valence
Bond
Theory
Table 5 |
1 | 4861-4864 | 5 Bonding in
Bonding in
Bonding in
Bonding in
Bonding in
Coordination
Coordination
Coordination
Coordination
Coordination
Compounds
Compounds
Compounds
Compounds
Compounds
5 5 1 Valence
Bond
Theory
Table 5 2: Number of Orbitals and Types of Hybridisations
4
sp
3
Tetrahedral
4
dsp
2
Square planar
5
sp
3d
Trigonal bipyramidal
6
sp
3d
2
Octahedral
6
d
2sp
3
Octahedral
Coordination
number
Type of
hybridisation
Distribution of hybrid
orbitals in space
Intext Questions
Intext Questions
Intext Questions
Intext Questions
Intext Questions
5 |
1 | 4862-4865 | 5 1 Valence
Bond
Theory
Table 5 2: Number of Orbitals and Types of Hybridisations
4
sp
3
Tetrahedral
4
dsp
2
Square planar
5
sp
3d
Trigonal bipyramidal
6
sp
3d
2
Octahedral
6
d
2sp
3
Octahedral
Coordination
number
Type of
hybridisation
Distribution of hybrid
orbitals in space
Intext Questions
Intext Questions
Intext Questions
Intext Questions
Intext Questions
5 3 Indicate the types of isomerism exhibited by the following complexes and
draw the structures for these isomers:
(i) K[Cr(H2O)2(C2O4)2
(ii) [Co(en)3]Cl3
(iii) [Co(NH3)5(NO2)](NO3)2
(iv) [Pt(NH3)(H2O)Cl2]
5 |
1 | 4863-4866 | 1 Valence
Bond
Theory
Table 5 2: Number of Orbitals and Types of Hybridisations
4
sp
3
Tetrahedral
4
dsp
2
Square planar
5
sp
3d
Trigonal bipyramidal
6
sp
3d
2
Octahedral
6
d
2sp
3
Octahedral
Coordination
number
Type of
hybridisation
Distribution of hybrid
orbitals in space
Intext Questions
Intext Questions
Intext Questions
Intext Questions
Intext Questions
5 3 Indicate the types of isomerism exhibited by the following complexes and
draw the structures for these isomers:
(i) K[Cr(H2O)2(C2O4)2
(ii) [Co(en)3]Cl3
(iii) [Co(NH3)5(NO2)](NO3)2
(iv) [Pt(NH3)(H2O)Cl2]
5 4 Give evidence that [Co(NH3)5Cl]SO4 and [Co(NH3)5(SO4)]Cl are ionisation
isomers |
1 | 4864-4867 | 2: Number of Orbitals and Types of Hybridisations
4
sp
3
Tetrahedral
4
dsp
2
Square planar
5
sp
3d
Trigonal bipyramidal
6
sp
3d
2
Octahedral
6
d
2sp
3
Octahedral
Coordination
number
Type of
hybridisation
Distribution of hybrid
orbitals in space
Intext Questions
Intext Questions
Intext Questions
Intext Questions
Intext Questions
5 3 Indicate the types of isomerism exhibited by the following complexes and
draw the structures for these isomers:
(i) K[Cr(H2O)2(C2O4)2
(ii) [Co(en)3]Cl3
(iii) [Co(NH3)5(NO2)](NO3)2
(iv) [Pt(NH3)(H2O)Cl2]
5 4 Give evidence that [Co(NH3)5Cl]SO4 and [Co(NH3)5(SO4)]Cl are ionisation
isomers Rationalised 2023-24
129
Coordination Compounds
It is usually possible to predict the geometry of a complex from
the knowledge of its
magnetic behaviour on
the basis of the valence
bond theory |
1 | 4865-4868 | 3 Indicate the types of isomerism exhibited by the following complexes and
draw the structures for these isomers:
(i) K[Cr(H2O)2(C2O4)2
(ii) [Co(en)3]Cl3
(iii) [Co(NH3)5(NO2)](NO3)2
(iv) [Pt(NH3)(H2O)Cl2]
5 4 Give evidence that [Co(NH3)5Cl]SO4 and [Co(NH3)5(SO4)]Cl are ionisation
isomers Rationalised 2023-24
129
Coordination Compounds
It is usually possible to predict the geometry of a complex from
the knowledge of its
magnetic behaviour on
the basis of the valence
bond theory In the diamagnetic
octahedral
complex,
[Co(NH3)6]
3+, the cobalt ion
is in +3 oxidation state
and has the electronic
configuration 3d
6 |
1 | 4866-4869 | 4 Give evidence that [Co(NH3)5Cl]SO4 and [Co(NH3)5(SO4)]Cl are ionisation
isomers Rationalised 2023-24
129
Coordination Compounds
It is usually possible to predict the geometry of a complex from
the knowledge of its
magnetic behaviour on
the basis of the valence
bond theory In the diamagnetic
octahedral
complex,
[Co(NH3)6]
3+, the cobalt ion
is in +3 oxidation state
and has the electronic
configuration 3d
6 The
hybridisation scheme is as
shown in diagram |
1 | 4867-4870 | Rationalised 2023-24
129
Coordination Compounds
It is usually possible to predict the geometry of a complex from
the knowledge of its
magnetic behaviour on
the basis of the valence
bond theory In the diamagnetic
octahedral
complex,
[Co(NH3)6]
3+, the cobalt ion
is in +3 oxidation state
and has the electronic
configuration 3d
6 The
hybridisation scheme is as
shown in diagram Orbitals of Co ion
3+
sp d
3
2
3+
hybridised
orbitals of Co
[CoF ]
(outer orbital or
high spin complex)
6
3–
Six pairs of electrons
from six F ions
–
3d
4s
4p
sp d
3
3 hybrid
4d
3d
3d
Six pairs of electrons, one from each NH3 molecule, occupy the six
hybrid orbitals |
1 | 4868-4871 | In the diamagnetic
octahedral
complex,
[Co(NH3)6]
3+, the cobalt ion
is in +3 oxidation state
and has the electronic
configuration 3d
6 The
hybridisation scheme is as
shown in diagram Orbitals of Co ion
3+
sp d
3
2
3+
hybridised
orbitals of Co
[CoF ]
(outer orbital or
high spin complex)
6
3–
Six pairs of electrons
from six F ions
–
3d
4s
4p
sp d
3
3 hybrid
4d
3d
3d
Six pairs of electrons, one from each NH3 molecule, occupy the six
hybrid orbitals Thus, the complex has octahedral geometry and is
diamagnetic because of the absence of unpaired electron |
1 | 4869-4872 | The
hybridisation scheme is as
shown in diagram Orbitals of Co ion
3+
sp d
3
2
3+
hybridised
orbitals of Co
[CoF ]
(outer orbital or
high spin complex)
6
3–
Six pairs of electrons
from six F ions
–
3d
4s
4p
sp d
3
3 hybrid
4d
3d
3d
Six pairs of electrons, one from each NH3 molecule, occupy the six
hybrid orbitals Thus, the complex has octahedral geometry and is
diamagnetic because of the absence of unpaired electron In the formation
of this complex, since the inner d orbital (3d) is used in hybridisation,
the complex, [Co(NH3)6]
3+ is called an inner orbital or low spin or spin
paired complex |
1 | 4870-4873 | Orbitals of Co ion
3+
sp d
3
2
3+
hybridised
orbitals of Co
[CoF ]
(outer orbital or
high spin complex)
6
3–
Six pairs of electrons
from six F ions
–
3d
4s
4p
sp d
3
3 hybrid
4d
3d
3d
Six pairs of electrons, one from each NH3 molecule, occupy the six
hybrid orbitals Thus, the complex has octahedral geometry and is
diamagnetic because of the absence of unpaired electron In the formation
of this complex, since the inner d orbital (3d) is used in hybridisation,
the complex, [Co(NH3)6]
3+ is called an inner orbital or low spin or spin
paired complex The paramagnetic octahedral complex, [CoF6]
3– uses
outer orbital (4d ) in hybridisation (sp
3d
2) |
1 | 4871-4874 | Thus, the complex has octahedral geometry and is
diamagnetic because of the absence of unpaired electron In the formation
of this complex, since the inner d orbital (3d) is used in hybridisation,
the complex, [Co(NH3)6]
3+ is called an inner orbital or low spin or spin
paired complex The paramagnetic octahedral complex, [CoF6]
3– uses
outer orbital (4d ) in hybridisation (sp
3d
2) It is thus called outer orbital
or high spin or spin free complex |
1 | 4872-4875 | In the formation
of this complex, since the inner d orbital (3d) is used in hybridisation,
the complex, [Co(NH3)6]
3+ is called an inner orbital or low spin or spin
paired complex The paramagnetic octahedral complex, [CoF6]
3– uses
outer orbital (4d ) in hybridisation (sp
3d
2) It is thus called outer orbital
or high spin or spin free complex Thus:
In tetrahedral complexes
one s and three p orbitals
are hybridised to form four
equivalent orbitals oriented
tetrahedrally |
1 | 4873-4876 | The paramagnetic octahedral complex, [CoF6]
3– uses
outer orbital (4d ) in hybridisation (sp
3d
2) It is thus called outer orbital
or high spin or spin free complex Thus:
In tetrahedral complexes
one s and three p orbitals
are hybridised to form four
equivalent orbitals oriented
tetrahedrally This is ill-
ustrated below for [NiCl4]
2- |
1 | 4874-4877 | It is thus called outer orbital
or high spin or spin free complex Thus:
In tetrahedral complexes
one s and three p orbitals
are hybridised to form four
equivalent orbitals oriented
tetrahedrally This is ill-
ustrated below for [NiCl4]
2- Here
nickel
is
in
+2
oxidation state and the ion
has
the
electronic
configuration
3d
8 |
1 | 4875-4878 | Thus:
In tetrahedral complexes
one s and three p orbitals
are hybridised to form four
equivalent orbitals oriented
tetrahedrally This is ill-
ustrated below for [NiCl4]
2- Here
nickel
is
in
+2
oxidation state and the ion
has
the
electronic
configuration
3d
8 The
hybridisation scheme is as
shown in diagram |
1 | 4876-4879 | This is ill-
ustrated below for [NiCl4]
2- Here
nickel
is
in
+2
oxidation state and the ion
has
the
electronic
configuration
3d
8 The
hybridisation scheme is as
shown in diagram Each Cl
– ion donates a pair of electrons |
1 | 4877-4880 | Here
nickel
is
in
+2
oxidation state and the ion
has
the
electronic
configuration
3d
8 The
hybridisation scheme is as
shown in diagram Each Cl
– ion donates a pair of electrons The compound is
paramagnetic since it contains two unpaired electrons |
1 | 4878-4881 | The
hybridisation scheme is as
shown in diagram Each Cl
– ion donates a pair of electrons The compound is
paramagnetic since it contains two unpaired electrons Similarly,
[Ni(CO)4] has tetrahedral geometry but is diamagnetic since nickel is in
zero oxidation state and contains no unpaired electron |
1 | 4879-4882 | Each Cl
– ion donates a pair of electrons The compound is
paramagnetic since it contains two unpaired electrons Similarly,
[Ni(CO)4] has tetrahedral geometry but is diamagnetic since nickel is in
zero oxidation state and contains no unpaired electron Rationalised 2023-24
130
Chemistry
Orbitals of Ni ion
2+
dsp hybridised
orbitals of Ni
2
2+
[Ni(CN) ]
(low spin complex)
4
2–
3d
4s
4p
Four pairs of electrons
from 4 CN groups
–
dsp
2 hydrid
3d
4p
3d
4p
5 |
1 | 4880-4883 | The compound is
paramagnetic since it contains two unpaired electrons Similarly,
[Ni(CO)4] has tetrahedral geometry but is diamagnetic since nickel is in
zero oxidation state and contains no unpaired electron Rationalised 2023-24
130
Chemistry
Orbitals of Ni ion
2+
dsp hybridised
orbitals of Ni
2
2+
[Ni(CN) ]
(low spin complex)
4
2–
3d
4s
4p
Four pairs of electrons
from 4 CN groups
–
dsp
2 hydrid
3d
4p
3d
4p
5 5 |
1 | 4881-4884 | Similarly,
[Ni(CO)4] has tetrahedral geometry but is diamagnetic since nickel is in
zero oxidation state and contains no unpaired electron Rationalised 2023-24
130
Chemistry
Orbitals of Ni ion
2+
dsp hybridised
orbitals of Ni
2
2+
[Ni(CN) ]
(low spin complex)
4
2–
3d
4s
4p
Four pairs of electrons
from 4 CN groups
–
dsp
2 hydrid
3d
4p
3d
4p
5 5 2 Magnetic
Properties
of
Coordination
Compounds
In the square planar complexes, the hybridisation involved is dsp
2 |
1 | 4882-4885 | Rationalised 2023-24
130
Chemistry
Orbitals of Ni ion
2+
dsp hybridised
orbitals of Ni
2
2+
[Ni(CN) ]
(low spin complex)
4
2–
3d
4s
4p
Four pairs of electrons
from 4 CN groups
–
dsp
2 hydrid
3d
4p
3d
4p
5 5 2 Magnetic
Properties
of
Coordination
Compounds
In the square planar complexes, the hybridisation involved is dsp
2 An example is [Ni(CN)4]
2– |
1 | 4883-4886 | 5 2 Magnetic
Properties
of
Coordination
Compounds
In the square planar complexes, the hybridisation involved is dsp
2 An example is [Ni(CN)4]
2– Here nickel is in +2 oxidation state and has
the electronic configuration 3d
8 |
1 | 4884-4887 | 2 Magnetic
Properties
of
Coordination
Compounds
In the square planar complexes, the hybridisation involved is dsp
2 An example is [Ni(CN)4]
2– Here nickel is in +2 oxidation state and has
the electronic configuration 3d
8 The hybridisation scheme is as shown
in diagram:
Each of the hybridised orbitals receives a pair of electrons from a
cyanide ion |
1 | 4885-4888 | An example is [Ni(CN)4]
2– Here nickel is in +2 oxidation state and has
the electronic configuration 3d
8 The hybridisation scheme is as shown
in diagram:
Each of the hybridised orbitals receives a pair of electrons from a
cyanide ion The compound is diamagnetic as evident from the absence
of unpaired electron |
1 | 4886-4889 | Here nickel is in +2 oxidation state and has
the electronic configuration 3d
8 The hybridisation scheme is as shown
in diagram:
Each of the hybridised orbitals receives a pair of electrons from a
cyanide ion The compound is diamagnetic as evident from the absence
of unpaired electron It is important to note that the hybrid orbitals do not actually exist |
1 | 4887-4890 | The hybridisation scheme is as shown
in diagram:
Each of the hybridised orbitals receives a pair of electrons from a
cyanide ion The compound is diamagnetic as evident from the absence
of unpaired electron It is important to note that the hybrid orbitals do not actually exist In fact, hybridisation is a mathematical manipulation of wave equation
for the atomic orbitals involved |
1 | 4888-4891 | The compound is diamagnetic as evident from the absence
of unpaired electron It is important to note that the hybrid orbitals do not actually exist In fact, hybridisation is a mathematical manipulation of wave equation
for the atomic orbitals involved The magnetic moment of coordination compounds can be measured
by the magnetic susceptibility experiments |
1 | 4889-4892 | It is important to note that the hybrid orbitals do not actually exist In fact, hybridisation is a mathematical manipulation of wave equation
for the atomic orbitals involved The magnetic moment of coordination compounds can be measured
by the magnetic susceptibility experiments The results can be used to
obtain information about the number of unpaired electrons and hence
structures adopted by metal complexes |
1 | 4890-4893 | In fact, hybridisation is a mathematical manipulation of wave equation
for the atomic orbitals involved The magnetic moment of coordination compounds can be measured
by the magnetic susceptibility experiments The results can be used to
obtain information about the number of unpaired electrons and hence
structures adopted by metal complexes A critical study of the magnetic data of coordination compounds of
metals of the first transition series reveals some complications |
1 | 4891-4894 | The magnetic moment of coordination compounds can be measured
by the magnetic susceptibility experiments The results can be used to
obtain information about the number of unpaired electrons and hence
structures adopted by metal complexes A critical study of the magnetic data of coordination compounds of
metals of the first transition series reveals some complications For
metal ions with upto three electrons in the d orbitals, like Ti
3+ (d
1); V
3+
(d
2); Cr
3+ (d
3); two vacant d orbitals are available for octahedral
hybridisation with 4s and 4p orbitals |
1 | 4892-4895 | The results can be used to
obtain information about the number of unpaired electrons and hence
structures adopted by metal complexes A critical study of the magnetic data of coordination compounds of
metals of the first transition series reveals some complications For
metal ions with upto three electrons in the d orbitals, like Ti
3+ (d
1); V
3+
(d
2); Cr
3+ (d
3); two vacant d orbitals are available for octahedral
hybridisation with 4s and 4p orbitals The magnetic behaviour of these
free ions and their coordination entities is similar |
1 | 4893-4896 | A critical study of the magnetic data of coordination compounds of
metals of the first transition series reveals some complications For
metal ions with upto three electrons in the d orbitals, like Ti
3+ (d
1); V
3+
(d
2); Cr
3+ (d
3); two vacant d orbitals are available for octahedral
hybridisation with 4s and 4p orbitals The magnetic behaviour of these
free ions and their coordination entities is similar When more than
three 3d electrons are present, the required pair of 3d orbitals for
octahedral hybridisation is not directly available (as a consequence of
Hund’s rule) |
1 | 4894-4897 | For
metal ions with upto three electrons in the d orbitals, like Ti
3+ (d
1); V
3+
(d
2); Cr
3+ (d
3); two vacant d orbitals are available for octahedral
hybridisation with 4s and 4p orbitals The magnetic behaviour of these
free ions and their coordination entities is similar When more than
three 3d electrons are present, the required pair of 3d orbitals for
octahedral hybridisation is not directly available (as a consequence of
Hund’s rule) Thus, for d
4 (Cr
2+, Mn
3+), d
5 (Mn
2+, Fe
3+), d
6 (Fe
2+, Co
3+)
cases, a vacant pair of d orbitals results only by pairing of 3d electrons
which leaves two, one and zero unpaired electrons, respectively |
1 | 4895-4898 | The magnetic behaviour of these
free ions and their coordination entities is similar When more than
three 3d electrons are present, the required pair of 3d orbitals for
octahedral hybridisation is not directly available (as a consequence of
Hund’s rule) Thus, for d
4 (Cr
2+, Mn
3+), d
5 (Mn
2+, Fe
3+), d
6 (Fe
2+, Co
3+)
cases, a vacant pair of d orbitals results only by pairing of 3d electrons
which leaves two, one and zero unpaired electrons, respectively The magnetic data agree with maximum spin pairing in many cases,
especially with coordination compounds containing d
6 ions |
1 | 4896-4899 | When more than
three 3d electrons are present, the required pair of 3d orbitals for
octahedral hybridisation is not directly available (as a consequence of
Hund’s rule) Thus, for d
4 (Cr
2+, Mn
3+), d
5 (Mn
2+, Fe
3+), d
6 (Fe
2+, Co
3+)
cases, a vacant pair of d orbitals results only by pairing of 3d electrons
which leaves two, one and zero unpaired electrons, respectively The magnetic data agree with maximum spin pairing in many cases,
especially with coordination compounds containing d
6 ions However,
with species containing d
4 and d
5 ions there are complications |
1 | 4897-4900 | Thus, for d
4 (Cr
2+, Mn
3+), d
5 (Mn
2+, Fe
3+), d
6 (Fe
2+, Co
3+)
cases, a vacant pair of d orbitals results only by pairing of 3d electrons
which leaves two, one and zero unpaired electrons, respectively The magnetic data agree with maximum spin pairing in many cases,
especially with coordination compounds containing d
6 ions However,
with species containing d
4 and d
5 ions there are complications [Mn(CN)6]
3–
has magnetic moment of two unpaired electrons while [MnCl6]
3– has a
paramagnetic moment of four unpaired electrons |
1 | 4898-4901 | The magnetic data agree with maximum spin pairing in many cases,
especially with coordination compounds containing d
6 ions However,
with species containing d
4 and d
5 ions there are complications [Mn(CN)6]
3–
has magnetic moment of two unpaired electrons while [MnCl6]
3– has a
paramagnetic moment of four unpaired electrons [Fe(CN)6]
3– has magnetic
moment of a single unpaired electron while [FeF6]
3– has a paramagnetic
moment of five unpaired electrons |
1 | 4899-4902 | However,
with species containing d
4 and d
5 ions there are complications [Mn(CN)6]
3–
has magnetic moment of two unpaired electrons while [MnCl6]
3– has a
paramagnetic moment of four unpaired electrons [Fe(CN)6]
3– has magnetic
moment of a single unpaired electron while [FeF6]
3– has a paramagnetic
moment of five unpaired electrons [CoF6]
3– is paramagnetic with four
unpaired electrons while [Co(C2O4)3]
3– is diamagnetic |
1 | 4900-4903 | [Mn(CN)6]
3–
has magnetic moment of two unpaired electrons while [MnCl6]
3– has a
paramagnetic moment of four unpaired electrons [Fe(CN)6]
3– has magnetic
moment of a single unpaired electron while [FeF6]
3– has a paramagnetic
moment of five unpaired electrons [CoF6]
3– is paramagnetic with four
unpaired electrons while [Co(C2O4)3]
3– is diamagnetic This apparent
anomaly is explained by valence bond theory in terms of formation of
inner orbital and outer orbital coordination entities |
1 | 4901-4904 | [Fe(CN)6]
3– has magnetic
moment of a single unpaired electron while [FeF6]
3– has a paramagnetic
moment of five unpaired electrons [CoF6]
3– is paramagnetic with four
unpaired electrons while [Co(C2O4)3]
3– is diamagnetic This apparent
anomaly is explained by valence bond theory in terms of formation of
inner orbital and outer orbital coordination entities [Mn(CN)6]
3–, [Fe(CN)6]
3–
and [Co(C2O4)3]
3– are inner orbital complexes involving d
2sp
3 hybridisation,
the former two complexes are paramagnetic and the latter diamagnetic |
1 | 4902-4905 | [CoF6]
3– is paramagnetic with four
unpaired electrons while [Co(C2O4)3]
3– is diamagnetic This apparent
anomaly is explained by valence bond theory in terms of formation of
inner orbital and outer orbital coordination entities [Mn(CN)6]
3–, [Fe(CN)6]
3–
and [Co(C2O4)3]
3– are inner orbital complexes involving d
2sp
3 hybridisation,
the former two complexes are paramagnetic and the latter diamagnetic On the other hand, [MnCl6]
3–, [FeF6]
3– and [CoF6-]
3– are outer orbital
complexes involving sp
3d
2
hybridisation and are paramagnetic
corresponding to four, five and four unpaired electrons |
1 | 4903-4906 | This apparent
anomaly is explained by valence bond theory in terms of formation of
inner orbital and outer orbital coordination entities [Mn(CN)6]
3–, [Fe(CN)6]
3–
and [Co(C2O4)3]
3– are inner orbital complexes involving d
2sp
3 hybridisation,
the former two complexes are paramagnetic and the latter diamagnetic On the other hand, [MnCl6]
3–, [FeF6]
3– and [CoF6-]
3– are outer orbital
complexes involving sp
3d
2
hybridisation and are paramagnetic
corresponding to four, five and four unpaired electrons Rationalised 2023-24
131
Coordination Compounds
The spin only magnetic moment of [MnBr4]
2– is 5 |
1 | 4904-4907 | [Mn(CN)6]
3–, [Fe(CN)6]
3–
and [Co(C2O4)3]
3– are inner orbital complexes involving d
2sp
3 hybridisation,
the former two complexes are paramagnetic and the latter diamagnetic On the other hand, [MnCl6]
3–, [FeF6]
3– and [CoF6-]
3– are outer orbital
complexes involving sp
3d
2
hybridisation and are paramagnetic
corresponding to four, five and four unpaired electrons Rationalised 2023-24
131
Coordination Compounds
The spin only magnetic moment of [MnBr4]
2– is 5 9 BM |
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