Ionisation isomers arise when an ionisable counter ion (simple ion) itself can act as a ligand. The exchange of such counter ions with one or more ligands in the coordination entity will result in ionisation isomers.

Ligands NH₃ AND Cl^-
Central metal Co (in cationic complex).

(i) Complex with co-ordination number 8 - Cu₂ [ZrF₈].
(ii) Complex with co-ordination number 7 - (NH₄)₃[ZrF₇].

Magnetic moment (μ) = \(\sqrt { n(n+2) } \) BM
Fe (z = 26) = 1s² 2s² 2p⁶ 3s² 3p⁶ 4s² 3d⁶
Fe²⁺ = 1s² 2s² 2p⁶ 3s² 3p⁶ 3d⁶ 4s⁰

∴μ =  \(\sqrt { n(n+2) } \) = \(\sqrt { 4(4+2) } =\sqrt { 24 } \) 
= 4. 89 BM  

Tetraammine copper (II) sulphate.

\({ }_{22} \mathrm{Ti}-{ }_{18}[\mathrm{Ar}] 4 \mathrm{s}^{2} 3 \mathrm{d}^{2} / {}_{21}\mathrm{Sc}-{ }_{18}[\mathrm{Ar}] 4 \mathrm{~s}^{2} 3 \mathrm{~d} \)
\({ }_{22} \mathrm{Ti}^{3+}-{ }_{18}[\mathrm{Ar}] 3 \mathrm{~d}^{1} /{ }_{18} \mathrm{Sc}^{3+}{ }_{18}[\mathrm{Ar}] 3 \mathrm{~d}^{0}\)
(i) In this complex the central metal ion is Ti³⁺, which has d¹ configuration. This single electron occupies one of the t_2g orbitals in the octahedral aqua ligand field. When white light falls on this complex the electron absorbs light and promotes itself to e_g level. The spectral data show the absorption maximum is at 20000 cm^-1 corresponding to the crystal field splitting energy \(\left(\Delta_{o}\right)\) 239.7 kJmol^-1. The transmitted colour associated with this absorption is purple and hence the complex appears purple in colour.
(ii) Thus in \(\left[\mathrm{Ti}\left(\mathrm{H}_{2} \mathrm{O}\right)_{6}\right]^{3+} \mathrm{d}-\mathrm{d}\) transition takes place.
(iii) But in \(\left[\mathrm{Sc}\left(\mathrm{H}_{2} \mathrm{O}\right)_{6}\right]^{3+} \mathrm{Sc}^{3+}\) has the outer electronic configuration of 3d⁰ where d-d transition is not possible and it is colourless.

Medicinal uses
(i) Ca-EDTA chelate, is used in the treatment of lead and radioactive poisoning.
(ii) That is for removing lead and radioactive metal ions from the body.
(iii) Cis-platin is used as an antitumor drug in cancer treatment.
Biological Importance compounds:-
(i) Fe²⁺ - porphyrin complex: It plays an important role in carrying oxygen from lungs to tissues and tissue carbon dioxide from to lungs.
(ii) Chlorophyll - useful in photosynthesis in plants.

\({ Ag }^{ + }2N{ H }_{ 3 }\rightleftharpoons { \left[ { Ag\left( { { NH }_{ 3 } } \right) }_{ 2 } \right] }^{ + }\)
\(k=\frac { { \left[ { Ag\left( { { NH }_{ 3 } } \right) }_{ 2 } \right] }^{ + } }{ \left[ { Ag }^{ + } \right] { \left[ { NH }^{ 3+ } \right] }^{ 2 } } \)
\(=\frac { \left[ { Ag }^{ + } \right] }{ { \left[ { Ag\left( { NH }_{ 3 } \right) }_{ 2 } \right] }^{ + } } =\frac { 1 }{ k{ \left( { NH }_{ 3 } \right) }^{ 2 } } \)
\(=\frac { 1 }{ 1.7\times { 10 }^{ 7 }\times { \left( 0.2 \right) }^{ 2 } } =\frac { { 10 }^{ -7 } }{ 1.7\times 4\times { 10 }^{ -2 } } \)
\(=\frac { { 10 }^{ -5 } }{ 6.8 } =1.47\times { 10 }^{ -5 }\)

In [CuCI₄]^-2 Cu²⁺, is reduced to Cu⁺ by I^-. Hence Cupric Iodide in converted to cuprous Iodide so [CuI₄]^-2 does not exist. In [CuCI₄]^-2 Cl^- cannot effect this change and so exists.

Addition of an alcoholic solution of dimethylglyoxime to an ammoniacal solution of Ni(II) gives rose - red precipitate Ni[ONCC N OH]₂ Nickel Cis (dimethylglyoximate)

(i) \(\mathrm{Mg}\left[\mathrm{Cr}\left(\mathrm{NH}_{3}\right) \mathrm{Cl}_{5}\right]^{2-} \rightleftharpoons \mathrm{Mg}^{2+}+\left[\mathrm{Cr}\left(\mathrm{NH}_{3}\right) \mathrm{Cl}_{5}\right]^{2-} (2 ions)\)
(ii) \(\begin{aligned} {\left[\mathrm{Cr}\left(\mathrm{NH}_3\right)_5 \mathrm{Cl}_3\left[\mathrm{CoF}_6\right]_2 \rightleftharpoons 3\right.} & {\left[\mathrm{Cr}\left(\mathrm{NH}_3\right)_5 \mathrm{Cl}\right]^{2+} } \\ & (5 \text { ions }) \end{aligned}\)\(+2\left[\mathrm{CoF}_6\right]^{3-}\)
(iii) \(\left[\mathrm{Cr}\left(\mathrm{NH}_{3}\right)_{3} \mathrm{Cl}_{3}\right]= \text{ No ions}\)
If no of ions increases, molar conductivity increases molar conductivity of the complex also INCREASES.
\(\therefore\) The order of the given compound is
[Cr(NH₃)₃Cl₃]<Mg[Cr(NH₃)₃Cl₃] < [Cr(NH₃)₅Cl₃] [CoF₆]₂
  (No ion)          (2 ions)                    (5 ions)

a) potassiumhexacyanidoferrate(II) - Potassiumhexacyanidoferrate(II) - K₄[Fe(CN)₆]
b) Pentacarbonyliron(0) - [Fe(CO)₅]
c) Pentaamminenitrito −kNcobalt(III)ion - [Co(NH₃)₅(NO₂)]²⁺
d) Hexaamminecobalt(III) Sulphate  - [CO(NH₃)₆](SO₄)₃
e) Sodiumtetrafluoridodihydroxidochromate(III)  - Na₂[CrF₄(OH)₂]

i) Na₂[Ni(EDTA)] - Sodium 2, 2', 2",2'" - (ethane-1,2 diyldinitrilo tetraacetatonickelate)(II)
ii) [Ag(CN)₂]^- - Dicyanido-kC-argentate (I) ion
iii) [CO(en)₃]₂(SO₄)₃ - Tris (ethane 1, 2 diamine)cobalt (III) sulphate
iv) [CO(ONO)(NH₃)₅]²⁺ - Pentaamminenitrito - KO cobalt (III) ion
v) [Pt(NH₃)₂Cl(NO₂)] - Diammainechloridonitro - kN - platinum (II)

[Co (en)₂ Cl₂]⁺ This is an octahedral complex

\(\text {(a) }\left[\mathrm{Cr}\left(\mathrm{NH}_{3}\right)_{6}\right]^{3+}:{ }_{24} \mathrm{Cr} \Rightarrow{ }_{18}[\mathrm{Ar}] 4 \mathrm{~s}^{2} 3 \mathrm{~d}^{4} \)
\({ }_{21} \mathrm{Cr}^{3+} \Rightarrow{ }_{18}[\mathrm{Ar}] 3 \mathrm{~d}^{3}\)

(i) d²sp³ hybridisation (octahedral)
(ii) It has three unpaired electrons (n = 3)
(iii) So it is paramagnetic
(iv) Magnetic moment \(\left(\mu_{\mathrm{s}}\right)=\sqrt{\mathrm{n}(\mathrm{n}+2)} \mathrm{BM}\)
\(=\sqrt{3(3+2)}=\sqrt{15}=3.87 \mathrm{BM}\)
\((b) \ \left[\mathrm{Ni}(\mathrm{CN})_{4}\right]^{2-:}{ }_{28} \mathrm{Ni} \Rightarrow[\mathrm{Ar}] 4 \mathrm{~s}^{2} 3 \mathrm{~d}^{8} ;{ }_{26} \mathrm{Ni}^{2+} \Rightarrow{ }_{18}[\mathrm{Ar}] 3 \mathrm{~d}^{8}\)

(i) dsp² hybridisation
(ii) Geometry - square planar
(iii) No unpaired electrons- It is Diamagnetic
(iv) Magnetic moment (μ_s) = 0.