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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