JEE (MAIN + ADVANCED)

XIII

INTRODUCTION
OF
CO-ORDINATION COMPOUNDS

INORGANIC CHEMISTRY BY PMS

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 INTRODUCTION OF CO-ORDINATION COMPOUND

INTRODUCTION OF CO-ORDINATION COMPOUNDS

ADDITION COMPOUND:
When aqueous solution of two or more than two salts is subjected to crystallize a new compound, which
contain ions of both salts, such compounds are called as addition compound / Adduct and reaction is
called addition reaction.
Salt1 (aq.) + Salt2 (aq.) crystalliz
 ation
 Addition compound / Adduct
addition reaction

Example : KCl (aq.) + MgCl2 (aq.) crystalliz

 ation
 KCl.MgCl2.6H2O
Carnallite
Example : KCN (aq.) + Fe(CN)2  4KCN . Fe(CN)2 or K4[Fe(CN)6]
Potassium Ferro cyanide

* TYPES OF ADDITION COMPOUNDS :

(1) Double salt : Completely ionize in aq. medium.All their ions can show in presence of aq. medium.
H2O
Example :KCl + MgCl2  KCl.MgCl2.6H2O K+ (aq.) + Mg2+(aq.) + Cl¯ (aq.)
Carnellite Number of ions = 5
Type of ions  3 (K+, Mg2+, Cl¯)
Example : Mohr’s salt FeSO4.(NH4)2SO4. 6H2O
Number of ions = 5
Types of ions  (Fe2+, NH4+, SO42–)  3
Example : Alum’s
General formula : M2SO4.N2(SO4)3.24H2O
[M(H2O)6]+ M  Monovalent  +1 (Na+, K+, Rb+, Cs+, NH4+)
(Except Li+)
[N(H2O)6]+3 N  Trivalent  + 3 (Cr+3, Al+3, Fe+3)
Type of ions = 3 (M+, N+3, SO42–)
Number of ions = 8
Example : Potash alum  K2SO4.Al2(SO4)3.24H2O

(2) Complex salt : Complex salts are the addition or molecular compounds which are formed bycombination
of two or more simple salts. There aqueous solution does not show the presence of all its constituent
ions, rather it show the presence of newly formed complex ion. That is some of ions loose their identity.
Ions which looses their identity in aqueous medium are written in square bracket collectively. Such ions
are called complex ions and compound containing such ions are called complex salt.
H 2O HO
Example : 4 KCN + Fe(CN)2  K4[Fe(CN)6] 2 4K+ (aq.) +[Fe(CN)6]4–(aq.)
Potassium Ferro cyanide
Theoretical Practical
No. of ions  11 5
Types of ions  3 2

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 INTRODUCTION OF CO-ORDINATION COMPOUND

* Coordination compounds : Central metal ion is surrounded by neutral molecule / ion. They act as
Lewis Base, are called ligands.
So complex formation is a lewis acid base reaction in which coordinate bond present between central
metal ion and ligands. So complex compound are also known as coordination compounds.

* In complex ion the metal atom or ion is present which is centre of complex ion act as Lewis acid is called
central metal ion [C.M.I.]

* Coordination number : Number of electron pairs (lone pairs) accepted by a central metal ion is called
coordination number of central metal ion.

* Denticity : Number of lone pair donated by a ligand simulataneously to a central metal ion is called its
denticity.

* Denticity is the property of ligand, while CN is the property of central metal ion.

* Charge on complex (ion) is sum of oxidation state of central metal ion and charge on ligand.

* Coordination polyhedra : Geometry around central metal ion is called coordination polyhedra.
example : Tetrahedral, square planar, octahedral etc.

* Coordination entity : Species inside the square bracket is called coordination entity.

* Coordination sphere : Space in 3D where coordinate bond formed between ligand and central metal
ion is called coordination sphere.

* Ionisation sphere: Space in 3D where complex ion form ionic bond with simple ions or complex ion is
called ionisation sphere.

* Species in coordination sphere are non-ionizable while species in ionisation sphere are ionizable.

* Counter ions : Simple ions which form ionic bond with complex ion are called counter ions.

Counter ions
C.M.I.
Ligands

K3 [Fe(CN)6] Coordination
Entity [Cu(NH3)4]SO4
No. of ligands
Coordination sphere

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 INTRODUCTION OF CO-ORDINATION COMPOUND

* CLASSIFICATION OF LIGANDS :

(1) On the basis of charge :

Cationic Anionic Neutral
NO  Nitrosonium/Nitrosylium
+ (Suffix) ide  ido / o General name is used
“ium” suffix is used in naming (Suffix) ate  ato O2:Dioxygen
N2H5+  Hydrazinium (Suffix) ite  ito N2: Dinitrogen
(Cl¯) Chloride  Chlorido PH3 :Phosphene
(SO42–) Sulphate  Sulphato PMe3:Trimethyl phosphene
(SO32–) Sulphite  Sulphito PPh3 :Triphenyl Phosphene
(CH3¯) Methyl  Methyl N2H4:Hydrazine
[No change in case of yl suffix] MeNH2: Methyl Amine
Except : H2O  Aqua
NH3 Ammine
CO  Carbonyl
NO  Nitrosyl

(2) On the basis of Denticity :

(A) Monodentate ligand :
* Having one donor sites
Example : NH3, NH2¯, NH–2, OH¯, F¯, Cl¯, Br¯, I¯, PH3, R2S, OR2 etc.

* Having two donor site

(I) Form 3-membered ring = unstable, therefore they act as monodentate ligand
(II) Formed (unstable) 4 members ring with central metal ions :
But as per requirement of C.N. of central metal ion they can act as bidentate. Such
monodentate ligands are called flexidentate ligand.
Example : Oxyanion having single central atom.
SO42– , SO32–, S2O32– , NO2¯, NO3¯ , PO43–, CO32–, CH3COO¯

O¯ O
O
Stability : M S MO¯– S = O
O¯ O O¯
[Cr(NH3)5(SO4  SO4 act as Monodentate
)]+ 2–

[Cr(NH3)4(SO4)]  SO42– act as Bidentate

+

(B) Bidentate ligand :Having 2 donor site but form 5, 6, 7, member ring are called bidentate.
H2N M
M N N
H2N

(en) or (ethylene-1,2-diamine) (dipy) or (dipyridine)

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 INTRODUCTION OF CO-ORDINATION COMPOUND

M
M
N N

–2
(Phen) or (Phenenthrolene) (Ox ) (Oxalate)
H3C
H2N
CH2 H2N
* M
M
C O¯
* H 2N
H3 C
O
–1
(bn) (Butylenediamine) (gly ) Glycinato
H3C H3C
C – O¯ C – O¯
HC M HC M
C=O C=O
H3C C6H5
–1 –1
acetylacetonato (acac ) Benzylactonate (bcac )
O–H
H3C N
C
M
C
H3C N
O¯
–1
dimethylglyoxinato (dmg )
(C) Polydentate ligands :
* Having 3-donar site  tridentate
NH2 NH2

H2C M CH2

H2C NH H2C
(dien) diethylenetriamine
* Having 4-donar site  tetradentate
CH2COO¯
NH–(CH2)2–NH
)2 CH2COO¯
(C

C
2 M
(H
H2

N M
)2

H2N H2N CH2COO¯

3–
(trien) triethylenetetraamine NTA (Nitritotriacetato)
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 INTRODUCTION OF CO-ORDINATION COMPOUND

* Having 5-donar site  pentadentate

NH2
CH2 CH2

CH2 – NH NH2
M CH2
CH2 – NH
NH–CH2
CH2 CH2
Teten (Tetraethylenepentaamine)

* Having 6-donar site  hexadentate

4–
EDTA (Ethylenediaminetetraacetato)

SPECIAL LIGANDS:

(1) AMBIDENTATE LIGANDS: Anionic ligands having two or more than two donor sites but uses
only one type of donar site at a time are called ambidentate ligand. In the naming of such ligands first
latter of donar site is written as suffix
Example: (i) CN¯ M  C  N¯ Cyanido-C
M  N  C Cyanido-N
(ii) OCN¯  Cyanato-O NCO¯  Cyanato-N
(iii) SCN¯  thiocyanato-S NCS¯  thiocyanato-N
(iv) NO2¯  Nitro, Nitrito-N NO2¯  Nitrito, Nitrito-O
(v) NOS¯  Thionitrito-N SON¯  Thionitrito-S
ONS¯  Thionitrito-O
(vi) SO32–  Sulphito-S OSO2–  Sulphito-O
(vii) O2S2O2–  thiosulphato (O, O’) OSSO22–  thiosulphato (O, S’)
(viii) O2C2S22–  dithiooxalato (O, O’) S2C2O22–  dithiooxalato (S, S’)

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 INTRODUCTION OF CO-ORDINATION COMPOUND

(2) CHELATING LIGANDS: Those ligands which form stable 5/6 membered ring structure with central
metal atom or ion during formtaion of complex are called Chelating ligands.
Number of chelate ring form by a ligand = denticity – 1
N
N (1) N
(3) M
[M(en)3]
N (2) N
N
Example : Ni(dmg)2 Rosy red ppt.

(H-bonding)
O--H–O

H 3C N N CH3
C 2+ C
Ni
C C
H 3C CH3
N N
O–H--O

(3) BRIDGING LIGANDS : In polynuclear complexes ligands joins two or more than two CMI. Such
ligands are written with µn prefix.where n = no. of CMI which are directly bounded with ligand.
2–
Cl¯ NH2¯ Cl¯
2+ 2+
Pt Pt

Cl¯ NH2¯ Cl¯

(4) ON THE BASES OF FIX AND VARIABLE CHARGE :

(1) Innocent : Having fix oxidation state e.g. : Cl¯, OH¯, H2O, en, NH3
(2) Non-Innocent : Can show different-different oxidation state.
E.g.: (O2)  O2, O2¯, O22–
(NO)  NO , NO+, NO¯
[unpaired electron]

[:N = O ]¯ [:N = O ] [:N  O:]

+
:
::

::

M M M
Bent Linear Linear
* They can be distinguished by :
(1) Bond order (2) Bond length / energy
(3) Number of unpaired electron (4) Geometry around doner side
(5) Configuration of central metal ion (6) Oxidation state of central metal ion
(7) Unpaired electron of central metal ion

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 INTRODUCTION OF CO-ORDINATION COMPOUND

CLASSIFICATION OF LIGANDS ON THE BASIS OF DONORAND ACCEPTOR PROPERTIES

OF THE LIGANDS :

Ligands

Classical Ligands (M  L) /

Non-classical Ligands (M L)
(Normal ligands) 
(-acid/-acceptor ligand)
When ligands can only donate their electron When ligands donate their electron pair
pair to the vacant orbital of the central metal to the vacant orbital of central metal atom/ion
atom/ion through coordinate bond are called and simultaneously accept electron pair from
classical (normal) ligands. filled orbital of central metal
– – – 2– – –
eg. H , OH , NH3, H2O, NH2 , NH , F , CH3 , atom/ion through back bond are called non-
C2H5–, MeNH2, -allyl, -cyclopentadienyl classical (-acid) ligands.

(-donor --acceptor ligand) (-donor - -acceptor ligand)


(M L) (M  L)
 
Example : Example :
CH2=CH2(–ethene)
+
CO, NO, NO , N2,
–
PPh3, PF3, CN , NO2¯ C6H6(–benzene)
CH2=CH–CH=CH2(–butadiene)

*-donor-acceptor : Such ligand share their lone pair of electron with vacant orbital of metal
and accept e– (pair) from filled d-orbital of metal into either their vacant
p/ d -atomic orbitals or vacant * (ABMO)

*-donor– -acceptor : They share their -e– with vacant orbital of metal and accept e– (pair)
from filled d-orbital of metal into their vacant *. So due to synergic
bonding metal ligand bond order increases . Such ligands are written
with prefix x, where x  hepticity of ligand which represent number
of donor atoms participating in donation

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 INTRODUCTION OF CO-ORDINATION COMPOUND

Ligand Bonding pattern No. of e– in No. of atom Name

donation in donation
 H
C
H
(1) C2H 4 M  H 2 2 2-ethylene or -ethylene
C
H

(2) CH2=CH–CH=CH2 CH2--CH--CH--CH2 4 4 4-butadiene or -butadiene



M

(3) C6H 6 M  6 6 6-Benzene or -Benzene

H
N
 H–B B–H
M 
(4) B3N3H6 H–N N–H 6 6 6-borazine or -borazine
B
H

(5) C 5 H5 ¯ (a) M  : 2 1 1- cp or -cp


Cyclopentadienyl (cp) (b) M 4 3 3- cp


(c) M 6 5 5- cp or -cp


 CH –CH=CH
(a) M  2 2
1 –
 – Allyl / -allyl (2e donor)
Allyl: CH2=CH–CH2 :
– – –
(b) CH2 -- CH -- CH2 (4e donor)
 
(6) C3H5
—

M
3 –
 – Allyl / -allyl (4e donor)

Cyclopropyl : : 1
M  – Cyclopropyl(2e donor)
–

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 INTRODUCTION OF CO-ORDINATION COMPOUND

CLASSIFICATION OF COMPLEX COMPOUNDS:

+ 0
(1) On the basis of charge  [ ] [ ]¯ [ ]
(Cation) (Anion) (Neutral)
so compound can be
(A) Simple cation + complex anion
(i) Fischer’s salt (Yellow ppt.)  K3[Co(NO2)6]
2 1
(ii) Sodium nitroprusside  Na 2 [Fe(CN)5 NO]

(B) Complex cation + simple anion

1 1
Brown ring complex  [Fe(H 2O)5 NO]SO 4
Switzer’s reagent  [Cu(NH3)4] SO4

(C) Complex cation + complex anion

[Cr(NH3)6] [Co(NO2)6]

(D) Neutral complex

Cisplatin (anti cancer drug)  cis - [Pt(NH3)2Cl2]
Wilkinson catalyst  [Rh(PPh3)3Cl]

(2) On the basis of central metal ion  On the basis of number of metals present in a coordination
sphere.
(A) Mono nuclear : having one central metal atom or ion
Example :Cisplatin , Fe(CO)5, K2 [PtCl6], [Ni(NH3)6]SO4, [Ag(NH3)2]Cl

(B) Binuclear : having two central metal atom or ion.

Example : Co2(CO)8 , Fe2(CO)9 , Mn2(CO)10
CO CO
CO CO
Co — Co
CO CO
CO CO
(C) Poly nuclear : having more than two central metal ion

[Be4O(CH3COO) 6]
CO CO Be
CO CO c
A
OA

Ru O
CO CO O OAc
c

CO Ru Ru CO Be Be
OAc
CO CO CO CO OA c
c
Be OA

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 INTRODUCTION OF CO-ORDINATION COMPOUND

(3) On the basis of types of ligand :

(A) Homoleptic : Only one type of ligand. e.g. : Fe(C5H5)2 , K3[Co(NO2)6]
(B) Hetroleptic : more than one type of ligand. e.g. : Na2[Fe(CN)5NO]

(4) On the basis of donation of ligand :

(A) -complex : having only lone pair donor
e.g.: cis-platin [Pt(NH3)2Cl2]

(B) -complex : having at least one -donor ligand present.

e.g. Cr (C6H6)2, Ferrocene Fe(C5H5)2 , Zeise’s salt K[PtCl3(2 – C2H4)]

(A) On the basis of stability :

M+x + nL  [MLn]+x
+x
[MLn]
KS Kf = +n n
Kf increase , forward reaction
[M ][L] tendency increase
Stability of complex formation increase
Stability
Formation , concentration of simple ion decrease
constant
constant
(A) Perfect Complex : Stable in presence of particular reagent having high value of Kf
(B) Imperfect complex : Unstable in presence of particular reagent having low value of Kf
CuSO4 + KCN Cu(CN)2 + K2SO4
(Redox reaction)
(IMR)

CuCN + (CN)2
(white ppt)

(excess) (KCN)
Perfect w.r.t.
H2S K3[Cu(CN)4]
H2S
No ppt.

CdSO4 + KCN Cd(CN)2

(No Redox) (white ppt)
(excess KCN)
Imperfect w.r.t.
H2S K2[Cd(CN)4]
H2S
CdS
(yellow)

* All ammonical complexes are imperfect in presence of acid.

H+
[Cu(NH3)4]+2 Cu+2 + NH3 NH4+

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 INTRODUCTION OF CO-ORDINATION COMPOUND

S. Ligand Ligand Name Comments (Flexidentate/Ambidentate/

No. Symmetrical / unsymmetrical)

1. H¯ Hydrido Mono

2. F¯ Flourido Mono

3. Cl¯ Chlorido Mono

4. Br¯ Bromido Mono

5. I¯ Iodido Mono

6. O22– Peroxido Mono

7. O2¯ Superoxido Mono, paramagnetic

8. O2– Oxido Mono

9. OH¯ Hydroxido Mono

10. CH3O¯ Methoxido Mono

11. OCN¯ Cyanato / Cyanato – O Mono , Ambi

12. NCO¯ Isocyanato / Cyanato–N Mono , Ambi

13. SCN¯ Thiocyanato / Thiocyanato–S Mono , Ambi

14. NCS¯ Isothiocyanato / Thiocyanato–N Mono , Ambi

15. SO42– Sulphato Mono , Flexi

16. SO32– Sulphito Mono, Ambi , Flexi

17 OSO22– Sulphito–O Mono, Ambi , Flexi

18. S2O32– Thiosulphato Mono, Ambi , Flexi

19. N3¯ , [NNN]¯ Azido Mono

20. N3– Nitrido Mono

21. NH2¯ Amido Mono

22. NH2– Imido Mono

23. NO2¯ Nitro / Nitrito–N Mono, Ambi , Flexi

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 INTRODUCTION OF CO-ORDINATION COMPOUND

S. Ligand Ligand Name Comments (Flexidentate/Ambidentate/

No. Symmetrical / unsymmetrical)

24. ONO¯ Nitrito / Nitrito–O Mono, Ambi , Flexi

25. NO3¯ Nitrato Mono , Flexi

26. CN¯ Cyanido Mono , Ambi

27. NC¯ Isocyanido Mono , Ambi

28. CH3COO¯ Acetato Mono , Flexi

29. C2O42– Oxylato Bidentate (Symm.)

30. CO32– Carbanoto Flexi , Mono

31. CH3¯ Methyl Mono

32. CH3CH2¯ Ethyl Mono

33. C6H5¯ Phenyl Mono

34. SnCl3¯ Trichlorostannito Mono

35. NH3 Ammine Mono

36. H2O Aqua Mono

37. CO Carbonyl Mono

38. NO Nitrosyl Mono, paramagnetic

39. O2 Dioxygen Mono, paramagnetic

40. N2 Dinitrogen Mono

41. PH3 Phosphene Mono

42. PMe3 Trimethyl phosphene Mono

43. PPh3 Triphenyl Phosphene Mono

44. N2H4 Hydrazine Mono

45 N2H2 Diazene/diimine/diimide Mono

46. MeNH2 Methyl Amine Mono

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 INTRODUCTION OF CO-ORDINATION COMPOUND

S. Ligand Ligand Name Comments (Flexidentate/Ambidentate/

No. Symmetrical / unsymmetrical)

47. EtNH2 Ethyl Amine Mono

48. NO+ Nitrosonium / Nitrosylium Mono

49. N2H5+ Hydrazinium Mono

50. Me2S Dimethylthioether Mono

51. Me2O Dimethylether Mono

52. PO43– Phosphoto Mono , Flexi

53. S2C2O22– Thiooxylato – S Symm , Ambi , 5-membered ring

54. O2C2S22– Thiooxylato – O Symm , Ambi , 5-membered ring

55. C2F4 Perflouroethene -Donar (2 elecron donar)

56. Pyridine Mono

N
57. NH2–CH2–CH2–NH2 Ethylenediamine Bidentate , Symmetrical , 5-membered ring

58. Dipyridine Bidentate , Symmetrical , 5-membered ring

N N
N N
59. Phenanthrolene Bidentate , Symmetrical , 5-membered ring

60. NH2–CH2–COO¯ Glycinato Bidentate , Symmetrical , 5-membered ring

CH 3–C=CH–C–CH 3
61. Acetyl acetonato (acac) Bidentate , Symmetrical , 6-membered ring
O¯ O

CH3–C=CH–C–Ph
62. O
Benzoylacetonato Bidentate , Unsymmetrical , 6-membered ring
O¯

63. PMe2–CH2–CH2–PMe2 1,2 Bis dimethyl Phosphino ethane Bidentate , Symmetrical , 5-membered ring

NH2–CH–CH–NH2
64. Butylenediamine Bidentate , Symmetrical , 5-membered ring, Optically active
H3C CH3

H2C–CH–CH3
65. Propylenediamine Bidentate , Unsymmetrical , 5-membered ring
H2N NH2

CH 3–C=N–OH
66. H 3C–C=N–O¯ DMG–1 (Dimethyl glyoximato) Bidentate , Unsymmetrical , 5-membered ring, NN-donar

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 INTRODUCTION OF CO-ORDINATION COMPOUND

S. Ligand Ligand Name Comments (Flexidentate/Ambidentate/

No. Symmetrical / unsymmetrical)
67. EDTA4– Ethylene diamine tetra acetato Hexadentate, 5-membered ring

68. NOS¯ Thionitrito – N Mono, Ambi , Flexi

69. SNO¯ Thionitrito – S Mono, Ambi , Flexi

70. ONS¯ Thionitrito – O Mono, Ambi , Flexi

71. CH2=CH2 Ethene / 2 – ethene -donar (2 electron donar)

72. -Cyclopentadienyl Mono

73. 3– Cyclopentadienyl -donar (4 electron donar)

74. 5– Cyclopentadienyl -donar (6 electron donar)

75. 6– Benzene -donar (6 electron donar)

H
H B H
N N
76. B B 6 – Borazine -donar (6 electron donar)
H N H
H


77. CH 2=CH–CH 2: -Allyl Mono (2 electron donar)

[CH2 CH CH2]
78. -Allyl / 3 Allyl -donar (4 electron donar)

CH2 CH CH CH2
79. 4 – Butadiene -donar (4 electron donar)

H
H
H
:

80. Cyclopropyl Mono

H H

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