Coordination Compounds

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Vishal Baghel

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CuSO4 + KCN? K2 [Cu (CN)4] + K2SO4

[Cu (H2O)4]2+ + 4CN-? [Cu (CN)4]2- + 4H2O

The coordination entity formed is K2 [Cu (CN)4] .

IUPAC name of the coordination entity is potassium tetracyanocuprate (II). It is a very stable complex. The copper atom present inside the coordination sphere does not separate out to form copper ions and cyanide ions due to strong bond between them.It does not ionize to give Cu2+ ions and hence on adding H2S, since there are no copper ions present so no precipitate of copper sulfide is formed.

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Vishal Baghel

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Copper sulphate exists as [Cu (H2O)4]SO4 . It is blue in colour due to presence of the [Cu (H2O)4]2+ ions.

When KF is added water is replaced by fluoride ion and green colour is due to [Cu (F)4]2- ions.

When KCl is added water is replaced by chloride ion and bright green colour is due to presence of [CuCl4]2- ions.

In both the cases water, weak field ligand is replaced by fluoride and chloride ions.

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Vishal Baghel

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There are four different types of ligands present in the complex. So, by fixing the position of 2 ligands we get 2 geometrical isomers and by changing the position of fixed isomer we get one more geometrical isomer.

Since it is tetrahedral complex so it should be optically active . But however it has not been possible to resolve optically active d and l forms of such a complex due to its complicated nature.

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Vishal Baghel

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Two types of ligand : chloride ion is unidentate ligand and -en (ethylenediamine) is bidentate ligand with two sites of attachment. The complexes in which two symmetrical bidentate chelating ligands AA and two monodentate ligands a, are coordinated to central metal atom M, exhibit the phenomenon of optical isomerism and can be resolved into their optical isomers.

An example of this type of complexes is given as shows both geometrical as well as optical isomerism. Its cis form is unsymmetrical, while the trans form is symmetrical because it contains a plane of symmetry. Hence, optical isomerism is shown by cis form.

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Vishal Baghel

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Optical isomers are the one which rotate the plane polarized light by a certain angle when passed through them and are mirror images of each other, also called as stereoisomer.

(i) C2O4 2- is a bidentate ligand so it can attach to central atom at two sites, forming a chelate ring. In the complexes of this type, three symmetrical bidentate chelating ligands AA are coordinated to the central metal atom M. Such complexes do not possess any element of symmetry and are optically active. Moreover, these complexes can be resolved into optical

 

(ii) In this complex Cl is an unidentate ligand with one site of attachment whereas -en (ethyle

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Vishal Baghel

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(i) No geometrical isomer is possible for [Cr (C2O4)3]3– because the ligand C2O 2- is bidentate ligand (which have two sites of attachment to the central atom) and also in the coordination sphere it is the only ligand bond to it.

 

(ii) In the coordination sphere of [Co (NH3)3Cl3] there are two types of ligands present i.e NH3 and Cl- . Coordination number is There are 2 isomers possible for the complex:

Facial: In this isomer one type of ligand say NH3 forms the face of the square bipyramidal (triangular) structure.

Meridional: In this isomer one type of ligand are along the central axis of the pyramidal structure.

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Vishal Baghel

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Isomers are the compounds which have same chemical formula but different arrangement of atoms in space. There are principle two types of isomerism:

(i) Stereo isomerism

(ii) Geometrical isomerism

(iii) Optical isomerism

(iv) Structural isomerism

(v) Ionisation isomerism

(vi) Linkage isomerism

(vii) Coordination isomerism

(viii) Solvate isomerism

Geometrical isomerism comes into existence by the different spatial arrangement of groups around the central metal atom. Similar groups may either be arranged on the same side or on opposite sides of the central metal atom. This gives rise to two types of isomers called cis and trans isomers. Wh

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Vishal Baghel

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(i) Starting with cation, the complex ion contains six ammonia molecules with cobalt in + 3 oxidation The name of compound: [Co (NH3)6]Cl3 is hexaamminecobalt (III) chloride.

 

(ii) The complex ion is cation, so there are 2 ammonia molecules, one chloride ion and methyammine molecule qith platinum in + 2 state. Going in alphabetical order, the name of compound: [Pt (NH3)2Cl (NH2CH3)]Cl is diamminechloridomethylammineplatinum (II)

 

(iii) It is a complex cation with six water molecules and titanium atom in + 3 state. The name of the compound: [Ti (H2O)6]3+ is hexaaquatitanium (III) ion

 

(iv) The complex ion is cation with

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Vishal Baghel

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(i) Tetrahydroxidozincate (II) = [Zn (OH)4]-2

Tetrahydroxi means 4 hydroxide ions with zinc in + 2 oxidation state. Hydroxide ions have a negative charge of -1, so balancing the overall charge of the coordination compound to be zero we get the formula as : [Zn (OH)4]-2

 

(ii) Potassium tetrachloridopalladate (II) = K3 [PdCl4].

Tetrachlorido means 3 Chloride ions each having a negative charge. Platinum is in + 2 state. Balance overall charge as 0, no. Of potassium ions are 3. Formula: K3 [PdCl4].

 

(iii) Diamminedichloridoplatinum (II) = [Pt (NH3)Cl2]2+

Diammine means 2 ammonia molecules, dichlorido means 2 chloride ions, platinum

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Vishal Baghel

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(i) Let Oxidation of Co be x and charge on the complex is given as + 2

H2O has Oxidation Number: 0

CN has Oxidation Number: -1

en has Oxidation Number :0

 

(ii) Let Oxidation number of Co be x and charge on the complex is given as + 1

Br has Oxidation number: 1

en has oxidation number : 0

 

(iii) Let Oxidation number of Pt be x and charge on the complex is given as -2

Cl has oxidation number : -1

 

(iv) This complex can also be seen as [Fe (CN)6]3-

Let Oxidation number of Fe be x and charge given on the complex is given as -3

CN has oxidation number : -1

(v) Let Oxidation number of Cr be x and charge given on the complex is given

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