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Compounds
Introduction :
(a) The concept of co-ordination compounds arises from the complex
formation tendency of transition elements.
(b) These compound play a vital role in our lives, as chlorophyll of plants
and haemoglobin of animal blood are also the co-ordination compounds
of Mg and Fe respectively.
COORDINATION COMPOUNDS :
If I have to live my Generally compounds of metals attached to group of neutral molecules/
life again, I would ions through coordinate bonds. It may be charged ion or a neutral
always remain in my species.
laboratory for the e.g. : [Cu(NH3)4] SO4
greatest joy of my life
to acccomplish orginal
scientificwork.
COORDINATION SPHERE :
Aggregate of metal and ligands attached to it is called coordination
sphere. It remains as a single unit in the solutions. Metal atom acts as
J. B. Andre Dumas Lewis acid and ligands act as Lewis base in these complexes.
e.g. : K4 [Fe(CN)6]
Ionic Co-ordination
sphere sphere
COORDINATION NUMBER :
The number of lone pairs accepted by a given central atom from ligands
(it may be different from number of ligands attached).
In [Cu(NH3)4]+2 the co-ordination no. of Cu is 4
In [Co(en)3]3+ , the co-ordination no. of cobalt is 6 and (en) is a bidentate
ligand.
LIGANDS :
(i) The neutral molecules, anions or cations which are directly
linked with central metal atom or ion in a complex ions are
called ligands.
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(ii) The ligands are attached to central metal ion or atom through co-ordinate bond or dative bond.
Some common polydentate ligands
Name abbreviation structure
ethylenediamine en (Bidentate)
2, 2-bipyridyl bipy
CH3–C–CH=C–CH3
acetylacetanato acac (Bidentate) || |
O O
..
..
oxalate ox (Bidentate) –OOC – COO–
dimethylglyoximate dmg
diethylenetriamine dien
triethylenetetramine trien
DENTICITY :
The number of atoms (sites) through which any ligand can attach to a metal atom is called its denticity.
Type of Ligand Definition Examples
Monodentate Ligands having only one H2O, NH3, CO, Cl–, CN–, ONO–
site of attachment
Multidentate Ligands having many sites (atoms) oxalate (C2O42–), biphenyl
through which these can attach to
central metal atom
Ambidentate Ligands which can attach a metal NO–2, OCN–
atom through more than one way / atom.
Bridging Ligands Ligands which can attached simultaneously OH–, NH2–
to more than one metal atoms.
(denoted by in nomenclature)
NOMENCLATURE :
Writing the name of a coordination compound :
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(a) The name of negative ligands end with – o.
F– Fluoro Br– Bromo Cl– Chloro SCN– Thiocyanato – S
– odo N3– Azido OH– Hydroxo NCS– Thiocyanato – N
H– Hydrido HS– Mercapto C2 O 42 Oxalato O2– Superoxo
O2– Oxo CN– Cyano S2– Sulphido
O22– Peroxo NO2– Nitro N3– Nitrido
(b) Neutral groups (no special ending)
NH3 Ammine H2O Aqua
CO Carbonyl NO Nitrosyl
en Ethylenediammine C5H5N Pyridine
(c) The name of positive ligands end with – ium.
NH2NH3+ Hydrazinium , NO+ Nitrosonium (or nitrosylium), NO2+ Nitronium
3. If there are several ligands of the same kind, the prefixes di, tri, tetra, penta and hexa are used to show
number of ligands of that type.
For example : [OsCl2(SO4)(NH3)3] Triamminedichlorosulphatoosmium (IV)
If the name of the ligands includes a number such as dipyridyl or ethylenediamine, then bis, tris and tetrakis
are used instead of di, tri and tetra and the name of ligands is placed in brackets.
For example : [TiCl4(C2H5OC2H5)2] Tetrachlorobis(diethylether)titanium(IV).
4. The oxidation state of the central metal is shown by a Roman numeral in brackets immediately following its
name. No gap should remain.
5. Complex cations and neutral molecules have no special ending but complex anions end in –ate.
For example : HgCl42– Tetrachloromercurate (II).
6. If ligand is attached through different atoms, then after the name of the ligands –Name of the atom through
which it is attached to central metal atom is written.
For example : [Zn(NCS)4]2+ Tetrathiocyanato–N–zinc()
[Cd(SCN)4]2+ Tetrathiocyanato–S–cadmium()
SOLVED EXAMPLE :
1. What is the coordination number of the central metal ions in the following complexes :
(i) [Cu(NH3)4]2+ (ii) [Fe(C2O4)3]3– (iii) [Pt Cl2(en)2]
(iv) [Mo(CN)8]4– (v) [Fe(EDTA)] – (vi) [Pd I2(ONO)2(H2O)2]
Sol. (i) NH3 is monodentate ligand
Points of attachment with Cu2+ = 4 × 1 = 4
C.N. of Cu2+ = 4
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(iii) ‘en’ is a bidentate ligand and Cl– is a monodentate ligand
Point of attachment with Pt2+ = 2 × 2 + 2 × 1 = 6
C.N. of Pt2+ = 6
2. Calculate the oxidation state of the central metal atom in the following :
(i) [CoCl(NH3)5]2+ (ii) K4 [Fe(CN)6]
(ii) Ni(CO)4 (iv) [Fe(EDTA)]–
Sol. (i) x + 5 × (0) – 1 = + 2
x=+2+1=3 Oxi. state of Co = + 3
(ii) 4 × (+1) + x + 6 × (– 1) = 0
or x = + 6 – 4 = + 2 Oxi. state of Fe = + 2
(iii) x + 4 × (0) = 0
or x = 0 Oxi. state of Ni = 0
(iv) x + 1 × (– 4) – 1 = 0
or x = + 4 – 1 = + 3 Oxi. state of Fe = + 3
3. Write the structural formula corresponding to each of the following IUPAC names :
(a) tetraamminedichlorocobalt (III) chloride
(b) dicyanoargentate (I) ion
(c) tris (ethylenediamine) copper (II) sulphate
(d) sodium diaquatetrahydroxoaluminate (III)
Sol. (a) [CoIIICl2(NH3)4]Cl (b) [AgI(CN)2]¯
(c) II
[Cu (en)3]SO4 (d) Na[AllII(OH)4(H2O)2]
UNSOLVED PROBLEMS :
5. Write the structural formula corresponding to each of the following IUPAC names :
(a) potassium tetracyanozincate (II)
(b) tetracarbonyl nickel (0)
(c) potassium tetracyanonickelate (0)
(d) potassium trioxalatoaluminate (III)
Ans (a) K2[ZnII(CN)4] (b) [Ni0(CO)4] (c) K4[Ni0(CN)4]
(d) lII
K3[Al (C2O4)3]
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6. Write IUPAC names of the following :
(a) [Cr(acac)3] (b) [V(H2O)6]Cl3
(c) (NH4)3[Co(C2O4)3] (d) K2 [CrO4]
Ans. (a) Tris (acetylacetanato) chromium (III)
(b) Hexaaquavanadium (III) chloride
(c) Ammonium trioxalatocobaltate (III)
(d) Potassium tetraoxochromate (VI)
UNSOLVED PROBLEM :
8. Determine the effective atomic number of the metal atom in the following :
(a) [Cr(CO)6] (b) [Fe(CN)6]3– (c) [Co(CN)6]4– (d) [Ni(NH3)6]2+
[Cr = 24 ; Fe = 26; Co = 27 and Ni = 28 as atomic numbers]
Ans. (a) 36 (b) 35 (c) 37 (d) 38
WERNER'S THEORY :
Several theories were proposed but none of them could satisfactorily explain the observed properties of
Co(III) ammines and of other similar compounds like Pt(IV) ammines which had been prepared by then. It
was only in 1893, that Werner presented a theory known as Werner's coordination theory which could
explain all the observed properties of complex compounds. More important postulates of this theory are :
Most element exhibit two types of valencies :
(a) Primary valency and (b) Secondary valency.
(a) Primary valency :
This corresponds to oxidation state of the metal ion. This is also called principal, ionisable or ionic
valency. It is satisfied by negative ions and its attachment with the central metal ion is shown by dotted lines.
(b) Secondary or auxiliary valency :
(i) It is also termed as coordination number (usually abbreviated as CN) of the central metal ion. It is non-ionic
or non-ionisable (i.e. coordinate covalent bond type). This is satisfied by either negative ions or neutral
molecules. The ligands which satisfy the coordination number are directly attached to the metal atom or ion
and shown by thick lines. These are directed towards fixed positions in space about the central metal ion,
and six ligands are arranged at the six corners of a regular octahedron with the metal ion at centre. This
postulate predicted the existence of different types of isomerism in coordination complexes.
(ii) Every element tends to satisfy both its primary and secondary valencies. In order to meet this requirement
a negative ion may often show a dual behaviour, i.e. it may satisfy both primary and secondary valencies
since in every case the fulfilment of coordination number of the central metal ion appears essential.
In all the ammines cobalt complexes, cobalt shows secondary valency (i.e. coordination number) of six and
primary valency (i.e., oxidation state) of three.
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SOLVED EXAMPLES :
9. Which of the following has the highest molar conductivity in solution :
(a*) [Pt(NH3)6]Cl4 (b) [PtCl(NH3)5]Cl3
(c) [PtCl2(NH3)4 ]Cl2 (d) All have same molar conductance
Sol. [Pt(NH3)6]Cl4 gives maximum number of ions in the solution and as number of ions increases molar
conductivity in solution increases.
UNSOLVED PROBLEMS :
10. A solution containing 0.319 gm of complex CrCl3 . 6H2O was passed through cation exchanger and the
solution given out was neutralised by 28.5 ml of 0.125 M NaOH. The correct formula of the complex will be
[mol. wt. of complex = 266.5]
(A) [CrCl(H2O)5]Cl2 . H2O (B) [Cr(H2O)6]Cl3 (C) [CrCl2(H2O)4]Cl. 2H2O (D) All are correct
Ans. B
11. Consider the following complexes :
(i) K2PtCl6 (ii) PtCl4 . 2NH3 (iii) PtCl4 . 3NH3 (iv) PtCl4 . 5NH3
Their electrical conductance in aqueous solution are :
(A) 256, 0, 97, 404 (B) 404, 0, 97, 256
(C) 256, 97, 0, 404 (D) 404, 97, 256, 0
Ans. A
CHELATE EFFECT :
A coordination compound having at least one multidentate ligand like EDTA forming ring complex is called
chelate.
The greater stability of the chelated complex in comparison to normal complex is called chelate effect.
Ex. Ni2+ (aq) + 6 NH3 (aq) [Ni(NH3)6]2+ (aq) Kformation = 108
Ni2+ (aq) + 3 NH2CH2CH2NH2(aq) [Ni(en)6]2+ (aq) Kformation = 1018
SOLVED EXAMPLE :
12. Explain why [Cu(en)2)2+ is less stable than [Fe(EDTA)]–?
Ans. [Cu(en)2]2+ has four membered rings in the structure. On the other hand [Fe(EDTA)]– has five membered
ring in the structure.
Greater is the number of rings of chelation, more is the stability of the complex
C.N (4)
Page # 6
o
C.N (6)
o
The state of hybridisation will be decided with the help of magnetic nature of complex (for most of the cases)
so we require additional information of magentic moment, = n (n 2) B.M, to calculate number of unpaired
electron.
Drawback of V.B.T.
(i) We can decide the geometry of the complex only on the basis of observed magentic nature of the
complex.
(ii) This theory does not give any idea about the nature of the ligand (wether it is weak or strong)
(iii) This theory does not give any idea about thermodynamic stability of the complex.
(iv) This theory does not give any idea about spectral properties of the complex.
METAL CARBONYLS :
Compounds of metals with CO as a ligand are called metal carbonyls.
They are of two types
(a) Monomeric : only one metal atom per molecule.
Example of monomeric carbonyls
[Ni(CO)4] sp3, tetrahedral
[Fe(CO)5 ] dsp3, trigonal bypyramidal
[Cr(CO)6] d2 sp3, octahedral
V(CO)6 d2 sp3, octahedral (only carbonyl which is paramagnetic having one unpaired
electron.This is least stable among all the four carbonyls)
(b) Polymeric : Two or more than two metal atom per molecule and they have metal-metal bonds.
eg. : Mn2 (CO)10 , Fe2(CO)9, etc.
UNSOLVED PROBLEM :
13. In metal carbonyls the metal carbon bond length is found to be less than the expected bond length. Explain
why ?
Energy correspond
to absorption
eg
metal 3/5 0 or + 0.6 0 average
atom/ion + 6L energy
0 2/5 0 or – 0.4 0 level
Average energy
t2g
of 'd' orbitals in presence
of ligand Energy correspond to
evolution of energy
[Crystal field splitting
for octahedral complex]
Page # 7
(b) C.F.T. for C.N. = 4 (Tetrahedral complexes)
t2g
metal + 2/5 = + 0.4
atom/ion + 4L
– 3/5 = – 0.6 t
Average energy of 'd' orbitals eg
in presence of ligand
4
t
9 0
Calculation of Crystal Field splitting energy (C.F.S.E)
Formula : CFSE = [– 0.6 n(eg) + 0.4 (n) (t2g)] t
where n & n are number of e–s in eg and t2g orbital respectively.
t = Crystal field splitting energy for tetrahedral complex
Spectrochemical series of ligands : Increasing strength of the ligands
I– < Br – < S–2 < SCN– < Cl– < NO3– < N3– < F– < OH– < C2O4–2 < H2O < NCS– < CH3CN < Py
weakest
< NH3 < en < NO2– < PPh3 < CN– < CO
Strongest
SOLVED EXAMPLES :
14. How would you account for the following :
(a) [Fe(CN6]3– is weakly paramagnetic while [Fe(CN6]4– is diamagnetic
(b) Ni(CO)4 possesses tetrahedral geometry while [Ni(CN)4]2– is square planar
Sol. (a) [Fe(CN)6]3– involves d2sp3 hybridization.
3d 4s 4p
Fe3+ (d5)
[Fe(CN)6]3–
[Fe(CN)6]4–
Ni(0)3d8
Ni(CO)4
In the formation of [Ni(CN)4]2–, Ni2+ ion undergoes dsp2 hybridization, hence it is square planar in shape.
Ni2+
[Ni(CN)4]2– Rearrangement 2
dsp hybridization
Page # 8
15. Explain the following :
(i) All the octahedral complexes of Ni2+ must be outer orbital complexes.
(ii) [CoF6]3– is paramagnetic but [Co(CN)6]3– is diamagnetic.
[CoF6]3–
In [Co(CN)6]3–, Co3+ undergoes d2sp3 hybridization. All electrons are paired. Hence, it is diamagnetic.
[Co(CN)6]3– `
UNSOLVED PROBLEM :
16. Find out the hybridization, geometry and magnetic moment of the complexes :
(a) [Co(NH3)6]3+ (b) [Cr(CN)6]3–
2 3
Ans. (a) d sp , octahedral, zero magnetic moment.
(b) d2 sp3 , octahedral, magnetic moment = 3.87.
17. The correct order for the CFSE (numerical value) for the following complexes is
Complex P Q R S
3– 3– 3+
Formula [CoF6] [Co(CN)6] [Co(NH3)6] [Co(H2O)6]3+
(A) P > Q > R > S (B) Q > R > S > P (C) S > R > P > Q (D) R > Q > P > S
Ans. (B)
ISOMERISM :
Isomers are built from the same set of atoms but have different "connectivities", that is, they are joined
together in different patterns.
In structural isomers , these patterns differ in the way the atoms are positioned in different parts of a
compound.
In stereoisomers, they differ in the way the ligands are positioned around the central atom of the complex.
Structural isomers :
These are of four types.
(i) Ionization isomers : It occurs when the ligand in the complex can be exchanged with the anions
outside the coordination sphere.
eg. : [Co(NH3)5Cl]SO4 and [Co(NH3)5SO4]Cl
(ii) Hydrate isomerism : This type of iosomerism arises when different number of water molecules are
present inside and outside the coordination sphere
eg. : [Cr(H2O)6]Cl3 & [Cr(H2O)5Cl]Cl2 . H2O
(iii) Linkage isomerism : In some ligands, there are two possible coordination sites. In such
cases, linkage isomerism exist. e.g., NO2 group can be bonded to metal ions through nitrogen (–
NO2) or through oxygen (–ONO). SCN too can be bonded through sulphur (–SCN) thiocyanate or
through nitrogen (–NCS) isothiocyanate
For example : [Co ONO (NH3)5] Cl2 & [Co NO2 (NH3)5] Cl2
(iv) Coordination isomerism : It occurs when both the cation and anions are complexes. In such
cases, the ligands and central metal atom or both can be exchanged.
For example : [Co(NH3)6] [Cr(CN)6] & [Cr(NH3)6 ][Co(CN)6]
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Stereoisomers :
These are of two types.
(i) Geometrical isomerism : It occurs when exchange of atoms or ions 'within' the coordination
sphere of the complex changes its geometry. It is possible in square planar & octahedral complexes.
For example : [Pt Cl2 (NH3)2 ] exists in 'cis' & 'trans' forms.
(ii) Optical isomerism : The complex compounds which are mirror images and are 'not' superimposable
are optical isomers. The complexes with coordination number equal to 6, having bidentate ligands
provide example of such isomers.
For example : [Co(en)3]3+
SOLVED EXAMPLES :
18. Which of the following is true :
(A) [Zn(Cl)2 (NH3)2] will exist in cis and trans forms
(B) [Pt(Br) (Cl) (NH3) (Py)] is an optically active compound
(C) The brown ring complex [Fe(H2O)5NO+]2+ is paramagnetic
(D) All the above are true
Sol. (C), (A) is tetrahedral (B) is square planar [Pt() complex] (C) is Fe() complex, contains three unpaired
electrons.
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(b) (CH3)4 Sn, (C2H5)4 Pb, Al2 (CH3)6, Al2 (C2H5)6 etc.
Bridging groups
Cl Cl
–1
+2
Fe
Ferrocene Fe (5 – C5H5)2
–1
Page # 11