Coordination(Complex) Compounds

Complex compounds belong to the class of addition compounds. Addition compounds are of two types.
Addtion Compounds:
1. Double Salts: eg KCl.MgCl2.6H2O(carnallite), K2SO4.Al2(SO4)3.24H2O(potash alum) etc.
Such compounds lose their identity in aqueous solution. They behave as if it is a mixture of two salts,
as same ions are produced
KCl.MgCl2.6H2O + aq. K+ + 3Cl– + Mg2+ + 6H2O
2. Coordination or complex compounds: Such compound is formed by the additon of two
compounds, but once it is formed, retains its unique identity in aqueous solution, which is different
from the individual compounds from which it is formed. The properties of complex are different from
both metal ion and ligands.
K4[Fe(CN)6] + aq. 4 K+ + [Fe(CN)6]4–
No doubt the compound has been formed by the addition of Fe(CN)2 with excess KCN, but once it is
formed it retains its uniqueness. It does not produce free CN–. In stead it contains a bulky ferrocyanide
ion [Fe(CN)6]4– which is called a complex ion. Such compounds are also called coordination compounds.

COMPLEX/Coordination Compounds:
A coordination compound can have a complex ion like the one discussed before or the molecule
itself is a neutral complex having no ion in it eg. [Ni(CO)4].
The complex consists of two parts:
(a) Central metal ion/atom (Lewis acid)
(b) Ligands (Lewis base)
The above two are put inside a square bracket [ ] and that region is called the Coordination
Sphere(CS) or Coordination entity. The term complex is derived from the fact that these are Lewis
acid–Lewis base complexes. The term coordination is derived from the fact that these contain coordinate
or dative bonds.

K4[Fe(CN)6] is a coordination compound which contains the anionic complex [Fe(CN)6]4– and 4K+
which are the couter ions. The complex ion contains
(a) Fe2+ : Central metal ion which accepts the electron pairs from ligands and hence act as Lewis
acid
(ii) Six CN– ions which are ligands which donate electron pairs to central metal ion and hence
acts as Lewis base
Note the charge of central metal ion and ligands are not shown, in stead the net charge of 4– is
shown for the complex ion.

[Ni(CO)4] is a neutral complex and there is no ion. Since CO molecules are neutral ligands, Ni atom is
in 0 oxidation state.

[Cu(NH3)4]SO4 is a coordination compound which contain cationic complex [Cu(NH3)4]2+ .

According the Valence Bond Theory(VBT), the ligands make coordinate covalent(dative) bonds with
the metal ion describing a fixed geometry. [Fe(CN)6]4– has an octahendral geometry while [Ni(CO)4]
has a tetrahedral geometry. The metal ion or atom uses vacant but hybrid orbitals(hence fixed geometry)
while the ligands use the filled orbitals(lone pairs) for the dative bonds. The details of bonding we shall
discuss later.
Coordination Number(CN): The number of metal–ligand covalent bonds is called CN of the complex.
For the complex [Fe(CN)6]4–, CN is 6 and for [Cu(NH3)4]2+ and [Ni(CO)4] it is 4.

Importance of Coordination Compounds: Most metals, more particularly the transition metals
form a number of complexes which have got great industrial and biochemical applications.

4-
[Fe(CN)6]
[Ni(CO)4]
-
CN
CO
Ni = central metal
2+
- - Fe : Central metal ion atom
CN CN - CO = ligand
CN : ligand
2+
Dative bond
Fe
Ni CO
-
- CN
CN OC

-
CN
Coordination Sphere CO
(Coordination Entity)
Tetrahendral geometry
Octahedral geometry

Werner’s Theory for Coordination Compounds:

Alfred Werner, a Swiss Nobel Laurate of 1913, introduced his famous theory on coordination compounds
in 1893 by working with several addition compounds like CoCl3.xNH3, PtCl4.xNH3, PtCl2.xNH3 etc.
His theory was based on the following observations.
(a) Chemical reactions of the ammonia complexes of metal ions like Pt4+, Pt2+, Co3+ with
precipitating agents like AgNO3.
(b) Conductance mesaurements of the these complexes
(d) Isomer Analysis of complexes having fixed composition but different properties(say
colour)
According to Werner there are two types of valencies for the complexex.
(1) Primary Valency :
* This is the charge or the Oxidation State(OS) of the central metal ion. In other
words the number of elctrons lost by the metal atom.
* This valency is non-directional as it is electrovalency. This valency is statisfied
by the negative ions present inside and outside the coordination sphere(CS).
2+ 4-
In ferrocyanide ion [Fe(CN)6] , Fe has a primary valency of 2, or more strictly +2.
In the complex, [CoCl2(NH3)4]Cl, the primary valency(OS) of Co is +3 which is satisfied by two Cl–
inside the coordination sphere and one Cl– outside the CS.
 (2) Secondary Valency:
* It is called the Coordination Number(CN) of the metal atom or ion of the complex.
It is the number of ligand–metal coordinate bonds.
* This is satsfied by the both neutral and ionic ligands present inside the CS.
In the example [CoCl2(NH3)4]Cl, the secondary valency(CN) is 6, out of which 4 are neutral NH3
molecules and two are Cl– ions.
* The secondary valency is directional as the bond is covalent. Hence the complex
has a fixed shape or geometry.

1. Chemical analysis and Conductivity Measurement by Werner:

Werner prepared several addition compounds of PtCl4 with NH3 having different colours, chemical
reactivity and conductivity. On the basis of his findings, it was revealed that these are different complexes
with different number of Cl– present inside and outside the CS. Only the Cl– ions present outside the CS
resulted the white precipitate with AgNO3 solution. The total number of ions produdced from one
molecule of the compound were also different, for which the conductivities were different. The table
below gives the formula of the complexes with the number of ions produced from one formula unit,
their conductivities, the number of free Cl– present outside CS which gives precipitate with AgNO3.

Formula as No. of Ions Conductivity No of free Formula of

Addition produced (Scm2 mol-1) Cl– precipited Complex
compound per formula
unit

PtCl4.6NH3 5 523 4 [Pt(NH3)6]Cl4

PtCl4.5NH3 4 404 3 [PtCl(NH3)5]Cl3
PtCl4.4NH3 3 299 2 [PtCl2(NH3)4]Cl2
PtCl4.3NH3 2 97 1 [PtCl3(NH3)3]Cl
PtCl4.2NH3 1 0 0 [PtCl3(NH3)3]

Note that the first complex [Pt(NH3)6]Cl4 contains five ions i.e one [Pt(NH3)6]4+ and four Cl– ions,
hence it showed maximum conductivity and resulted four moles of AgCl precipitate with one mole of
the complex. The last compound [PtCl3(NH3)3] has no ion and shows no conductivity and also no
precipiate with AgNO3 as there is no free Cl– outside the CS.
Subsequently complexes like [PtCl5(NH3)]– and [PtCl6]2– were prepared as their monopotassium and
dipotassium salts respectively.
Conclusion: In all the complexes, the CN was found to be 6(secondary valency) while the OS of the
metal atom(primary valency) is +4.
Similar analyses were made with Co3+ and complexes of other metal ions. Four CoCl3.xNH3 complexes
are given below.
[Co(NH3)6]Cl3 : Orange Yellow(Four ions); [CoCl(NH3)5]Cl2 : Red (Three ions)
[Co(NH3)4Cl2]Cl : Purple (two ions) [CoCl3(NH3)3] : Green (no ion)

2. Isomer Analysis:
(a) On anaysing the NH3 complex with CoCl3, he found two different compounds having same
formula [CoCl2(NH3)4]+ with different colours. Later on, he discovered that they were geometrical
isomers cis and trans compounds with different spatial arrangements of the ligands. The details about
isomerism will be discussed later.
 Cis- [CoCl2(NH3)4]+ : Red Trans- [CoCl2(NH3)4]+ : Green
This led to the understanding that the geometry of the complexes were octahedral rather than hexagonal
or trigonal prism which were the alternative geometries for CN=6. The latter two geometries have three
possible geometrical forms, while the octahedral has only two forms that were actually shown by the
complexes.
(b) [PtCl2(NH3)2] gave two complexes having different properties.
(a) Cis-Platin : an anti-carcinogen (b) Trans-Platin : no biological response
This suggested that the geometry is square planar, not tetrahedral. Only the square planar geometry can
have to different geometrical form cis and trans(to be discussed later).

Types of Ligands on the basis denticity and charge type:

Denticity of a ligand is the number of coordinating atoms present in one molecule of the ligand. On that
basis, the ligands can be classifed as follows.
Ligands can be anionc, neutral or cationic.
1. Monodentate(Unidentate/ one-toothed): One donor atom.
Monodentate Anionic Ligands with name:
F– fluorido(fluoro) NO2– nitrito-N(nitro) (nitrogen donor)
– –
Cl chlorido (chloro) ONO nitrito-O(nitrito) (oxygen donor)
– –
Br bromido(bromo) NO3 nitrato
I– iodido (iodo) CH3COO– : acetato
S2– sulphido(sulpho) CN– cyanido(cyano) (carbon donor)
–
NH2 amido NC– isocyanido(isocyano) (nitrogen donor)
OH– hydroxido(hydroxo) SCN– thiocyanato (sulphur donor)
– –
H hydrido NCS isothiocyanato (nitrogen donor)
O2– oxido(oxo)
O22– peroxido(peroxo) N3– azido

(N.B: According to latest IUPAC nomenclature, the suffix ‘e’ of an anion is replaced by ‘o’ . The old
names of the ligands are given inside parentheses)
Monodentate Neutral Ligands with name:
H2O aqua(aquo) NH3 ammine CO carbonyl
C5H5N pyridine(py) CS thiocarbonyl NO nitrosyl
O2 dioxygen N2 dinitrogen Ph3P triphenylphosphine
Monodentate Cationic Ligands with names:
NO+ (nitrosonium/nitrosylium) Cl+(Chloronium)

2. Bidentate(two-toothed) : Two donor atoms

CH2 CH2
Examples: Ethylene diamine(en) : H2N NH2 (neutral)

O O
2–
Oxalato: (ox) C O (C2O4)2– (anionic)
O O
 O NH2
Glycinato(gly)1– C CH2 (anionic)
O

O O
C
Carbonato(CO32–) (anionic)
O

O O
Acetylacetonato(acac)1– (anionic)
CH3 C CH C CH3

(enolate of acytelacetone)
1–
Benzoylacetonato(beac) (anionic)

O O O O
Ph C CH C CH3 Ph C CH C CH3

Biipyridine(bipy) : (2,2’-bipyridine) (netural)

N N

Phenanthroline(phen) : (netural)
N N

CH3
CH2 CH
Propylene diamine(pn) H2 N (propane-1,2-diamine)
NH2

(neutral)

O
OH
N N
Dimethyl glyoximato(dmgH)1– (anionic)
CH3 C C CH3

Sulphato SO42– (anionic)

2–
Thiosulphato S2O3 (anionic)
Urea NH2-CO-NH2 (neutral)
Thiourea NH2-CS-NH2 (neutral)
3. Tridentate(three toothed) : Three donor atoms

CH2 CH2
CH2
NH CH2
Examples: Diethylene triamine(dien) : H2N (neutral)
NH2

N
Terpyridine(Terpy) : (neutral)
N N

4. Tetradentate : Four donor atoms

CH2
CH2 CH2
NH CH2 CH2
Examples: Triethylene tetraamine(trien): H N CH2 NH
2
NH2

(netural)
Macrocyclic polydentate Ligands:
Porphyrins: (substituted porphines): This is an example of a macrocyclic tetradentate
ligand. Cyclam, Crown ethers are also examples of such ligands. In crown ethers, the prefix number is
the ring size and the suffix number is the number of oxygen atoms like 12-crown-4. There are also 15-
corwn-5, 18-crown-6 etc. containing 5 and 6 oxygen atoms respectively(not shown here).

NH NH NH O O
N
N

(porphine) NH NH O O
NH

cyclam 12-crown-4

(N.B: Chlorophyll and hemoglobin are complexes of porphyrines)

5. Pentadentate : Five donor atoms

O O O
O P O P O P O
Example: Tripolyphosphato : (anionic)
O O O

(N.B: This ligand binds the Ca2+ and Mg2+ present in hard water)
 6. Hexadentate : Six donor atoms
Example: Ethylene diamine tetraacetato (EDTA)4–

O O
O C CH2 CH2 C O
N CH2 CH2 N
O C CH2
CH2 C O (anionic)
O
O

7. Octadentate: Eight donor atoms.

Example: Diethylene triamine pentaacetato (DTPA)5– (anionic)

Some terminology for Ligands:

1. Chelating Ligands: Polydentate ligands form cyclic complexes called Chelates. Hence these ligands
are called chelating ligands. eg. en, trien, ox, gly etc. These ligands form form stable complexes(chelates)
than monodentate ligands having identical donor atoms.

2. Amidentate Ligands: Monodentate ligands having two alternative sites for coordination.
Ex: CN–: cyanido(C-donor), NC–: isocyanido(N-donor)
NO2– nitrito-N(N-donor); ONO– : nitrito-O(O-donor)
SCN : thiocyanato(S-donor); NCS– : isothiocyanto (N-donor)
–

OCN–: cyanato(O-donor); NCO : isocyanato (N-donor)

3. Flexidentate Ligands:
Polydentate ligands using different number of ligand sites(donor atoms) in different compounds.
SO42– : (a) one donor atom: [Co(SO4)(NH3)5]+ (Co-III) CN=6
+
(b) two donor atoms: [Co(SO4)(en)2] (Co-III) CN=6
–
EDTA : (a) 5 donor atoms: [Cr(OH)(HEDTA)] (Cr-III) (HEDTA)3– CN =6
(b) 4 donor atoms: [Pd(H2EDTA)] (Pd-II) (H2EDTA)2– CN=4

4. Macrocyclic Ligands: Polydentate ligands which are themselves cyclic are called macrocyclic ligands.
Porphine is an example of such ligands. Chlorophyll and haemoglobin are examples of macorocyclic
complexes. Such complexes are even more stable than chelates.

Types of Ligands on the basis of donor/acceptor properties:

(You can better understand this classification after studying Ligand Field Theory)
  (sigma) donor ligands:: Those ligands which can only donate only nonbonding electron
pairs(called -orbitals) to the metal ion, e.g. H2O, NH3, en, etc. They cannot form -bonds( discussed
later). These are ligands are intermediate field ligands.
(2)  (sigma) donor and  (pi) accepter ligands: Those ligands which can donate nonbonding
pair to form -bond with metal and also can accept electron pair using their empty antibonding 
molecular orbitals (MO). Such ligands can involve in backbonding ( bond) with the metal ion. For
example CO, CN–, NO, NO2- etc. These ligands contain multiple bonds. These are strong field ligands.
(3)  (sigma) donor and  (pi) donor ligands: Ligands like I–, Br–, S2–, O2–, N3–, RO–, F– belong to this
catetory. They form -bonds alongwith sigma. They donate electron pair to the metal ion to form -
bonds in addition to forming -bonds. These are weak field ligands.
IUPAC Nomenclature of Complex compounds:
(A) Cationic Complexes:
Ligands in alphabetical order metal in English(OS in Roman) anion

First the ligands are arranged in alphabetic order follwed by the name of the metal in English
wtih the OS of the metal in Roman given inside parenthesis after the name of the metal. This is to be
followed by the name of the anion(counter ion).
Examples:
(i) [CoCl(CN)(NH3)2(H2O)2]2SO4 : diamminediaquachloridocyanidocobalt(III)sulphate
+3 -1 -1 -2
[CoCl(CN)(NH3 )2 (H2O)2 ]2SO4 (Ammine and aqua are neutral ligands)
N.B: The multiplying suffixes di, tri, tetra ..... or bis, tris, tetrakis.....chosen are similar to the IUPAC
for organic nomenclature.
(ii) [Cr(ox)(NH3)4]Br : tetraammineoxalatochromium(III)bromide
+3 -2 -1
[Cr(ox)(NH3)4]Br CN=6
(iii) [Fe(NO2)(CO)(en)2]SO4 : carbonylbis(ethylene diamine)nitrito(N)iron(III)sulphate
+3 -1 -2
[Fe(NO2)(CO)(en)2]SO4 CN =6
(iv) [Cr(en)3](NO3)2 : tris(ethylene diamine)chromium(II)nitrate (CN=6)

(v)[Cu(H2O)4]2+ : tetraaquacopper(II) ion

(B) Neutral Complexes:

Naming is similar to cationic complex, except that in neutral complex there is no anion.

(i) [Fe(gly)(ONO)(H2O)3] : triaquaglycinatonitrito(O)iron(II)

+2 -1 -1
[Fe(gly)(ONO)(H2 O)3 ] CN=6
(ii) [Fe(CO)5] : pentacarbonyliron(0)
(iii) [PtCl2(en)] : dichloridoethylene diamineplatinum(II)

(C) Anionic Complexes:

Cation(counter ion) Ligands in alphabetical order metal in Latin with
suffix ‘ate’ in place of ium/um(OS in Roman)

First the name of cation is written. Then the ligands are written in alphabetical order followed
by the name of metal in Latin (such as Ferrum, Argentum, Plumbum, Aurum etc) with suffix ‘ate’ in
place of ‘um’ or ‘ium’ if any (eg ferrate, argentate, plumbate, aurate etc.) This is followed by the OS of
the metal in Roman inside parenthesis.
(i) K4[Fe(CN)6] : potassium hexacyanidoferrate(II)
Common name: potassium ferrocyanide
 (ii) K2[Cu(CN)2(ONO)(NH3)] : potassium amminedicyanidonitrito(O)cuprate(I)
+2 +1 -2 -1
K 2[Cu(CN)2(ONO)(NH3)] CN=4
(iii) K[Ag(CN)2] : potassium dicyanidoargentate(I)
(iv) K2[Co(CO3)(gly)(ox)(CO)] : potassium carbonatocarbonylglycinatooxalatocobaltate(III)
+2 +3 -2 -1 -2
K 2[Co(CO3)(gly)(ox)(CO)] CN=6, CO32– acting as flexidentate ligand(here one-toothed)
(v) K[AuCl4] : potassium tetrachloridoaurate(III)
(vi) Li[AlH4] : lithium tetrahydridoaluminate(III) (common: Lithium Aluminium Hydride)

SAQ 1: Give the IUPAC names of the following.Also give the CN of the metal atom/ion in the compelx.
(i) [Ni(CO)4] (ii) K3[Fe(CN)5(H2O)] (iii) K3[Cu(CN)4]
(iv) K2[HgI4] (v) [Cr(C2O4)(ONO)(H2O)2(CO)]
(vi) K2[Ni(CN)4] (vii) [CoBr2(en)2]2SO4 (viii) K3[Co(NO2)6]
(ix) [Mo(CO)6] (x) K2[Gd(DTPA)(H2O)]
SAQ 2: Give the IUPAC names of the following complexes and give CN of metal ions.
(i) [Fe(ONO)(NO)(SO4)(en)] (ii) K2[CrCl2(CN)(NO2)(NH3)(H2O)]
(iii) [Ru(gly)(en)2]Cl2 (iv) [Fe(C5H5)2]

Solutions for SAQ 1:

(i) tetracarbonylnickel(0) (CN=4) (ii) potassium aquapentacyanidoferrate((II) (CN=6)
(iii) potassium tetracyanidocuprate(I) (CN=4)
(iv)potassium tetraiodidomercurate(II) (CN =4) (Exception : Latin name not used for Hg)
(v) diaquacarbonylnitrito(O)oxalatochromium(III) (CN=6)
(vi) potassium tetracyanidonickelate(II) (CN=4)
(vii) dibromidobis(ethylene diamine)cobalt(III)sulphate (CN=6)
(viii) potassium hexanitrito(N)cobaltate(III) (CN=6)
(ix) hexacarbonylmolybdenum(0) (CN=6)
(x) potassium aquadiethylene triaminepentaacetatogadolinate(III) (CN=9)

Writing Formula from Name:

The formula of a complex is written in a different order than its name. The chemical symbol of the
metal center is written first. The ligands are written next, with anionic ligands coming before neutral
ligands. If there is more than one anionic or neutral ligands, they are written in alphabetical with respect to the
first letter in their chemical formula(not name). The counter ion is written as required with its subscript.
Example: potassium diammineaquadichloridocyanidonitrito(N)chromate(II)
K2[CrCl2(CN)(NO2)(H2O)(NH3)]
SAQ 3 : Write the formula of the following complexes.
(i) Amminetetraaquachromium(II) (ii)Amminesulfatochromium(II)
(iii)Amminetetraaquachromium(II) sulfate (iv) Potassium hexacyanoferrate(III)
Solution: (i) [Cr(H2O)4(NH3)]2+ (it is cationic complex and the counter ion not given. CN=5)
(ii) [Cr(SO4)(NH3)] (It is a neutral complex, CN=3 )
(iii) [Cr(H2O)4(NH3)]SO4 (iv) K4[Fe(CN)6]

18-Electron Rule: (Noble Gas Rule) :

 (Note: Please study this after covering theories of metal-ligand bonding)
The number of valence electron in the complex should be less than equal to 18 in order to be a
stable complex.
[(n–1) d -electrons + n s -electrons(if any) + 2  CN ]  18
Example: (i) [Fe(CN)6]4–: Fe2+ : 3d6 4s0 Valence electrons = 6 + 2
8 2
(ii) [Ni(CO)4] : Ni(0) : 3d 4s : Valence electrons = 10 + 2 4 = 18
So the above complexes satisfiy the 18-electron rule. There are some which do not satisfy the 18-
electron rule as exceptional cases.
Ex: [Co(NH3)6]2+ : Co2+ : 3d7 4s0 : Valence electrons = 7 + 2  6 = 19
Therefore this complex have lower stability than its Co3+ counterpart which satisfies 18e rule.

Effective Atomic Number(EAN):

EAN = Atomic Number of metal(Z) – Oxdiation State of metal + 2  CN
For stable complex, the EAN should be equal to the electronic configuration of a noble gas.
[Fe(CN)6]4–: EAN = 26 – 2 + 12 = 36 ( Kr)
[Fe(CN)6]3–: EAN = 26 – 3 + 12 = 35
(N.B: EAN rule has been outdated as many stable complexes do not have EAN equal to the atomic
number of a noble gas. In the above examples, ferricyanide ion is more stable than ferrocyanide ion.)

Another way of classification of Complexes:

(a) Homoleptic : Complex containing ony one type of ligands: eg [Fe(CN)6]4–, [Cr(en)3]3+ etc
(b) Heteroleptic : Complex containing more than one type of ligand. eg [Fe(NH3)3Cl3]
(c) Isoleptic : Two complexes having different metal ions but same ligands and CN. eg
[Co(NH3)3Cl3] and [Cr(NH3)3Cl3].

STRUCTURAL ISOMERISM
There are six types of structural isomerism for inorganic complexes described below
1. Ionisation Isomerism: The isomers differ in the nature of ions produced in aqueous solution.
(a) [CrBr(NH3)5]SO4 (I) and [Cu(SO4)(NH3)5]Br (II)
(I) does not produce free Br–, instead there is free SO42– counterion to give white precipitate with BaCl2.
The second complex(II) does not produce free SO42– ion, instead produce free Br– to give yellowish
precipitate with AgNO3.
(b) [CoCl2(NH3)4]NO2 and [CoCl(NO2)(NH3)4]Cl
2. Hydrate Isomerism: The isomers differ in the number of H2O molecules present inside and
outside the coordination sphere.
[Cr(H2O)6]Cl3 (violet)(I) [CrCl(H2O)5]Cl2.H2O (blue green) (monohydrate) (II)
[CrCl2(H2O)4]Cl.2H2O (green) (dihydrate) (III)
(I) does not dehdyrate by a dehdyrating agent, in stead gives three moles of AgCl with excess AgNO3
solution. (II) loses one mole of H2O with a dehydrating agent like H2SO4 and also gives two moles of
AgCl with excess AgNO3. (III) loses two moles of H2O and gives only one mole of AgCl.
3. Linkage Isomerism(Bond Isomerism): The isomers differ in the nature of donor atoms in
ambidentate ligands.
(a) [Co(ONO)(NH3)5]SO4 (nitrito-O complex) and
[Co(NO2)(NH3)5]SO4 (nitrito-N complex)
(b) [Pd(SCN)2(en)2] (thiocyanato complelx) and
[Pd(NCS)2(en)2] (isothiocyanto complex)
4. Coordination Isomerism: This isomerism is shown by compounds having both cationic and anionic
complex parts. Some or all of the ligands are interchanged between cationic and anionic parts in thes isomers.
(a) [Cr(NH3)6][Co(CN)6] hexaamminechromium(III)hexacyanidocobaltate(III)
and [Co(NH3)6][Cr(CN)6] hexaamminecobtalt(III)hexacyanidochromate(III)
(b) [Cu(NH3)4][PtCl4] tetraamminecopper(II)tetrachloridoplatinate(II)
and [Pt(NH3)4][CuCl4] tetraammineplatinum(II)tetrachloridocuprate(II)
5. Coordination Position isomerism: This is shown by polynuclear complexes containing more
than one metal ion. Such complexes have bridging ligands between the metal ions. Such ligands are
prefixed with the symbol .
In such isomers some ligands interchange between the two metal ions.
-1 2+
NH2
+3 +3 -2
(NH3 )4 Co Co(NH3)2Cl2

-1
(unsymmetrical)
OH

tetraamminecobalt(III)--amido--hydroxidodiamminedichloridocobalt(III)
2+
NH2

Cl(NH3)3 Co Co(NH3 )3Cl

(symmetrical)
OH

triamminechloridocobalt(III)--amido--hydroxidotriamminechloridocobalt(III)
OR hexaamminedichlorido--amido--hydroxidodicobalt(III)

6. Ligand Isomerism: When isomeric ligands are used, the complexes are called ligand isomers.

NH2 NH2
(i) CH2 CH2 CH2 (trimethylene diamine or propane-1,3-diamine) (tn)

NH2 NH2
CH2 CH CH3
(propylene diamine or propane-1,2-diamine) (pn)

Complexes containing pn and tn ligands are ligand isomers.

Ex: [Co(pn)2Cl2]+ and [Co(tn)2Cl2]+
(ii) ortho, meta and para methylanilines can form ligand isomers with a metal ion.

7. Polymerisation Isomerism: This can approximately be called isomers, as their empirical

formulas are same though their molecular formulas are different. The isomers have the following general
formula. Strictly isomers have same moleccular formula. In this case, their empirical formula are same.
[MLm]n where n = 1, 2, 3 .....
[Co(NO2)3(NH3)3] n =1
[Co(NH3)6\][Co(NO2)6] n =2
[Co(NO2)2(NH3)4][Co(NO2)4(NH3)2] n =2
[Co(NO2)(NH3)5][Co(NO2)4(NH3)2]2 n=3
 Stereoisomerism
(I) Geometrical Isomerism (Diastereoisomerism)
(A) CN=4 (SQUARE PLANAR COMPLEX):

1. [Ma2b2] type : ( 2 GIs - Cis and Trans) (a, b are monodentate ligands)

a a a b

M M

b b b a

Cis Trans
Example: [PtCl2(NH3)2] cis-platin and trans-platin [Pd(NO2)2(NH3)2] (cis and trans)

2. [Ma2bc] type : (2 GIs - cis and trans) (a, b, c are monodentate ligands)

a a a c

M M

b c b a
(cis) (trans)

Ex; [PtCl2(NH3)(Py)]

3. [Mabcd] type: (3 GIs) (a, b, c, d are monodentate ligands)

The three GIs can be drawn by keeping any one ligand fixed at a particular position and placing
the other three ligands in the opposite position w.r.t the fixed ligand successively.

a b a c a b

M M M

d c d b c d

Ex: [Pt(NO2)(NH3)(NH2OH)(Py)+ amminehydroxylaminenitrito(N)pyridinepltatinum((II)

4. [M(AB)2 type : ( 2 GIs - cis and trans)

(AB is an unsymmetrical bidentate ligand with different donors, eg. glycinato)

A A A B
M M
B B B A
cis trans
Example: [Pt(gly)2] : diglycinatoplatinum(II)

N:B : Tetrahedral complexes(CN=4) do not show geometrical isomerism. They can show optical optical
isomerism.
(B) CN=6 (OCTAHEDRAL COMPLEX)

1. [Ma4b2] type : ( 2 GIs) (a, b are monodentate ligands)

b b
a b a a

M M

a a a a

a b
cis trans

Ex: [CoCl2(NH3)4]+ :

2. [Ma4bc] type: (2 GIs) (c is another monodentate ligand)

b
b
a c a a

M M

a a a a

a c
cis trans

Ex: [CoCl(NO2)(NH3)4]+

3. [Ma3b3] type : ( 2 GIs) Example: [CoCl3(NH3)3]

a a
a a a b
M M
b b b a
b
b
fac (cis )
mer (trans)

Fac (Facial) : In fac isomer, the three idential groups lie in a plane which does pass through the metal.
Mer(Meridional) : In mer isomer, the three identical groups lie in a place which passes through metal.

4. [Ma3b2c] type : ( 3 GIs)

Fac(cis) : 1 Mer(trans) : 2

a
a
a
a a a c a b
M M M
b c b a b a

b b c
fac(cis) mer(trans )-I m er(trans )-II
Mark the difference between the two mer isomers. In (I), b,b are on same side while in (II) they are on the
opoosite sides.
Ex. [CoCl2(NO2)(NH3)3] triamminedichloridonitrito-N-cobalt(III)

5. [Ma3bcd] type : (4 GIs)

Fac(cis) : 1 Mer(trans) : 3

a a a
a
a a a d a b
a d
M M M M

b d b a c a c a

c c b d
m er(trans)-I m er(trans )-II m er(trans )-III
fac(cis)

In the three mers, you will find that the three groups b, c and d are alternately remainly opposite to each
other.
Ex: [CoCl(CN)(NO2)(NH3)3]

6. [M(AA)2a2] type: ( 2 GIs) (AA is a symmetrical bidentate ligand like en)

A A

a A a A
M M
a A a
A

A A
cis trans

Ex: [CoCl2(en)2]+ dichloridobis(ethylenediamine)cobalt(III)

7. [M(AA)2ab] type: ( 2 GIs)

A A

a A a A
M M
b A A b

A A
cis trans

Ex : [CoCl(NH3)(en)2]2+
8. [M(AA)a2b2] type: ( 3 GIs)
Cis - 1; Trans- 2

a a b

a A b A a A
M M M
b A b A a A

b a b
cis trans-I trans-II

Ex: [CoCl2(NH3)2(en)]+

(N.B: Bidentate ligand always remain in cis position)

9. [M(AA)a2bc] type ( 3 GIS) Ex. [CoClBr(ox)(H2O)2]–
a b a

b A a A b A
M M M
c A a A a A

a c c

Thefirst two are trans and the last one is cis. This is similar to [M(AA)a2b2] type.

10. [M(AA)a3b] type: (2 GIs)

a a

a A a A
M M
a A b A

b a
fac(cis) mer(trans)

Ex: [CoCl3(ONO)(en)]–
11. [M(AB)3] type: (2 GIs) (AB= unsymm. bidentate ligand like glycinato)
A A

B B B A
M M
A A A B

B B
fac(cis) mer(trans)

Ex: [Cr(gly)3] tris(glycinato)chromium(III)

12. [Ma2b2c2] type: (5 GIs)

(a) cis-cis-cis (b) cis-cis-trans (c) cis-trans-cis

(d) trans-cis-cis (e) trans-trans-trans
(N.B: cis-trans-trans and trans-trans-cis are not possible)

a c b a a

a b a b a c b c b c

M M M M M
c b a b a c b c c b
c c b a a
cis-cis-cis cis-cis-trans cis -trans-cis trans -cis -cis trans-trans-trans

Ex: [CoCl2(NO2)2(NH3)2]–

13. [Ma2b2cd} type: 6 GIs

(structures not drawn)
14. [Ma2bcde] type: 9 GIs
(structures not drawn)
15. [Mabcdef] type: 15 GIs (each of them exists as d/l pair)
Ex: [PtBrClI(NO2)(NH3)Py]
16. [M(AB)2a2] type: 5 GIs
17. [M(AB)2ab] type: 6 GIs
18. [M(AAA)2] type: 2 GIs (fac and mer) [Co(dien)2]3+
19. [M(AAA)a3] type: 2 GIs (fac and mer) (AAA= symmetrical tridentate ligand like dien)
20. [M(AAA)abc]type: 6 GIs (fac=3, mer=3)
21. [M(AAAA)a2] type: 3 GIs (AAAA= symm. tetradentate ligand like trien)
22. [M(AA)(BC)de]: 5 GIs
23. [M(AA)(BB)cd] : 5 GIs
 OPTICAL ISOMERISM
Some of the GIs are disymmetric and hence chiral. They exist as d/l pair. Some complexes only show
enantimerism.

(A) CN=6(OCTAHEDRAL COMPLEX)

1. [Ma2b2c2] type: Only the cis-cis-cis isomer is chiral.

cis-cis-cis
a a
a b b a

M M
c b b c
c c

d/l pair

The other four GIs are achiral.

So total number of stereoisomers for [Ma2b2c2] type of complex = 5 + 1 = 6

2. [Ma3bcd] type: Only the fac(cis) is optically active and exists as d/l pair.
(the figure not shown)
Total number of stereoisomers for [Ma3bcd] type = 4 + 1 = 5

3. [M(AA)2a2] type: Only the cis isomer is chiral.

A A

A a a A
M M
A a a A

A A
d/l pair

The trans GI is achiral.

Hence total number of stereoisomers for [M(AA)2a2] type = 2 +1 = 3

4. [M(AA)2ab] type: Only the cis isomer optical active and exist
Similar to the previous case. Total number = 2+ 1 =3
Hence total number of stereoisomers for [M(AA)2ab] type = 2 +1 = 3
5. [M(AA)a2b2] type: Only the cis isomer is optically active. The other two trans ismoers are
inactive.
a a

a A A a
M M
b A A b

b b
d/l pair

Total number of stereoisomers for M(AA)a2b2] type:= 3 + 1 = 4

6. [M(AB)3] type : Both fac(cis) and mer(trans) are optically active.

cis trans
A A A A

B B B B A B B A
M M M M
A A A A B A A B

B B B B
d/l pair d/l pair

Total number of stereoisomers for [M(AB)3] type = 2 + 2 = 4

7. [M(AA)3] type:
A A

A A A A
M M
A A A A

A A
d/l pair

Ex: [Cr(en)3]3+ , [Cr(acac)3]2-

N.B: Such compound does not show geometrical isomerism.

8. [M(AA)2BB] type:
This also exists as d/l pair like the previous case.
Ex: [Co(ox)(en)2]+

(B) Square Planar Complexes(CN=4)

(i) Usually SP complexes are achiral as they are planar. But if such complexes carries a chiral
ligand, then the complexes exists as d/l pair. Exceptionally some of SP complexes go non-planar due to
ot her substutents. Example for the lat ter type is [Pd(isobutylenediamine)(meso-
diphenylethylenediamine)]2+ complex lacks planarity and becomes chiral and exists as d/l pair. Pt also
gives similar complex.
 (ii)Complexes having EDTA ligand:
Such complexes with Pd2+ are tetracoordinated(CN=4) and are square planar. Two CH2COO–
groups are free. This exists as d/l pair. Note that EDTA is a flexidentate ligand.
Ex: [(Pd(EDTA)]2–.

(C) Tetrahdral Complexes(CN=4)

Metal bonded to four different groups [Mabcd] type in Td geometry are chiral. But their
examples are rare. They undergo rapid racemisation.
Ex: [As(CH3)(C2H5)(S)(C6H5COO]2–
However some Td complexes of [M(AB)2] type are disymmetric and exits as a resolvable d/l
pair.
Ex: [Cu(beac)2], [Be(acac)2] (beac = benzoylacetonato; acac = acetylacetonato)

(D) Polynuclear Complexes:

Such complexes are also chiral and exist as d/l pair. (GI 2 + EP 1 = 3). One meso and the other
d/l pair.

E. Complexes having chiral ligands: [M(AA)(BB)*a2] type :

NH2 NH2
(pn) This is a chiral bidentate ligand.
CH3 CH CH2
[Co(NO2)2(en)(pn)*]
This has two cis and two trans GIs. Each of the two cis forms exists as a d/l pair. So a total of 6
stereoisomers exist in this compound.
Table showing number of Stereoisomers for Octahedral Complex with monodentate ligands

[Ma4b2] [Ma4bc] [Ma3b3] [Ma3b2c] [Ma3bcd]

No. of GIs
(Diastereoisomers) 2 2 2 3 4

No. of enantiomeric – – – – 1
pair
_______________________________________________________
Total no. of
Stereoisomers 2 2 2 3 5

[Ma2b2c2] [Ma2b2cd] [Ma2bcde] [Mabcdef]

No. of GIs
(Diastereoisomers) 5 6 9 15

No. of enantiomeric 1 2 6 15
pair
_______________________________________________________
Total no. of
Stereoisomers 6 8 15 30

Table showing Number of Stereoisomers for complexes having Bidentate ligands

[M(AA)2a2] [M(AA)2ab] [M(AA)a2b2] [M(AA)a2bc] [M(AB)3]

No. of GIs
(Diastereoisomers) 2 2 3 3 2

No. of enantiomeric 1 1 1 1 2
pair
_______________________________________________________
Total no. of
Stereoisomers 3 2 4 4 4

[M(AA)(BC)de] [M(AB)2cd] [M(AB)(CD)ef]

No. of GIs
(Diastereoisomers) 5 6 10

No. of enantiomeric 5 5 10
pair
_______________________________________________________
Total no. of
Stereoisomers 10 11 20

SAQ: How many isomers the following complexes have ?

(a) [CrBrCl(NH3)4]Br (b) [CrBr(NO2)(NH3)4]NO2
Solution: (a) 2 ionzation isomers(structural) + 2 geometrical isomers(diastereoisomers) = 4 isomers.

(b) 2 linkage isomers(NO2 and ONO) + 2 geometrical isomers = 4 isomers

 Theories of Metal-Ligand Bonding
(A) Valence Bond Theory(VBT):
According to VBT, the ligands uses lone pair oribitals to overlap with the vacant hybrid orbitals
of the central metal. Hybridization of the central metal atom is the key factor in VBT. Metal acts as
Lewis acid(electron acceptor) and the ligands act as Lewis bases(electron donor) to form coordinate
covalent(dative) bonds. VBT helps in predicting the shape, and magnetic properties(magnetic moment)
of most complexes.

The fixed geometry(shape) of a complex is determined from the hydridisation of the vacant
orbitals namely (n-1)d, ns, np and nd orbitals.
CN-2 : ML2 : Ex. [Ag(NH3)2]+, [Au(CN)2]– etc.: It is common for d10 metal ions like Ag+, Au+, Cu+,
Hg2+.
Hybridisation of the metal orbitals: sp
Shape : linear
CN-3: ML3 : Ex. [HgI3]– . It is also rare and is found in d10 metal ions like Hg2+, Cu+.
Hybridisation : sp2 Shape : Trigonal Planar

CN-4 : ML4. Examples are abundant. This has two geometries.

(a) Tetrahedral : sp3 hybridisation eg. [Zn(NH3)4]2+, [NiCl4]2–, [Ni(CO)4] etc
(b) Square Planar : dsp2 hybridsation eg. [Ni(CN)4]2–, [PtCl4]2– etc

CN-5 : ML5 : eg. [Fe(CO)5], [CoCl5]2–; ;Examples are rare.

Hybridisation: dsp3 or sp3d.
Shape: (a) trigonal bipyramidal (b) square pyramidal
In many cases the pentacoordinate complexes are distorted in between the two shapes.

CN-6 : ML6 : [Co(en)3]3+, [Fe(H2O)6]2+, [Cr(NH3)6]3+ etc.

Examples are abundant.
Hybridisation: d2sp3 or sp3d2 Shape: Octahderal or distorted octahderal
Rarely the shape can be trigonal prism.
CN-7 : ML7 : 2nd and 3rd row TM and Ln and An form complexes with CN=7. Examples are rarer
than CN=6 and CN=4.
Hybridisation: d3sp3 or sp3d3
Shape: pentagonal bipyramidal, capped octahedral, capped trigonal prism
Ex: [ZrF7]3–.
CN-8 : ML8; Formed mostly by heavier metal ions.
Shape: Square antiprism or dodecahedral or cubic
Ex: [ReF8]2– square antiprism [Mo(CN)8]4– : dodecahedron
CN-9 : ML9 : Formed by heavier metals. Ex. [Nd(H2O)9]3+.
Shape: Tricapped trigonal prism. Ex: [ReH9]2–.
(N.B: CN of 10, 11 and 12 are also there which are extremely rare)

We shall discuss in details about the CN=6 and CN=4 which are very abundantly available.
OCTAHEDRAL COMPLEX(CN=6)
There are two types of octahedral complexes.
(a) Inner Orbital Complex(IOC)/ Low Spin Complex:
(b) Outer Orbital Complex(OOC)/High Spin Complex:

(A) INNER ORBITAL COMPLEX(IOC):

(i) Strong Field ligands form IOC. Ligands having Carbon and Nitrogen donors are strong.
Examples: CO, CN–, NH3, NO2–, en etc.
(N.B: From a common point of view carbon and nitrogen donors are stronger bases than oxygen and
halogen donors due to lower electronegativities of former types. The actual cause will be discussed
later)
(ii) The metal atom uses two inner (n–1)d orbitals namely d x 2  y 2 and d z 2 are used alongwith one
ns and three np orbitals to undergo d2sp3 hybridisation.
(iii) If these two orbitals are not vacant, internal pairing of electrons occur in the (n-1)d orbitals
to the extent that is required to produce two empty orbitals.
(iv) Since the number of unpaired electrons get reduced by pairing, these complexes are called
LOW SPIN(LS) complexes or Spin Paired complexes.

Example 1: [Fe(CN)6]4–: OS of Fe = +2
EC: Fe : [Ar] 3d6 4s2 Fe2+ : [Ar] 3d6 4s0

Fe2+: 3d 4s 4p

3d 4s 4p
\
[Fe(CN)6]4–:
d2sp3 hy.
Magnetic property: Diamgagnetic

The four unpaired electrons present in 3d orbitals get paired to produce two vacant orbitals.
d2sp3 hybridisation takes place to form six hybrid oribitals describing octahedral geometry. The six
ligands use their lone pair oribitals(-orbitals) to overlap with these hybrid orbitals to form six dative
bonds. The (**) symbol prespresents the electron pairs from ligands. Since there is no unpaired electron,
it is diamagnetic.

Example 2 : [Fe(CN)6]3– OS of Fe = +3
Fe3+ : [Ar] 3d54s0

Fe3+ :
3d 4s 4p

3d 4s 4p
[Fe(CN)6]3–
d2sp3 hy.

Magnetic Property: Paramagnetic (No. of unpaired electrons = 1)

 Spin maganetic Moment() = n(n  2) BM = 3 BM
Since the number of unpaired electrons get reduced these complexes are called LOW SPIN(LS)
complexes.

Example 3 : [Mn(CN)6]3– OS of Mn = +3
Mn(25) : [Ar] 3d54s2 Mn3+ : [Ar]3d4 4s0

Mn3+
3d 4s 4p

3d 4s 4p
[Mn(CN)6]3–
d2sp3 hy.

Magnetic Property : Paramagnetic (No. of unpaired electrons = 2)

In this case, complete pairing is not required and the number of unpaired electrons is reduced to 2.

Example 4 : [Cr(en)3]3+ OS of Cr = +3
Cr(24) : [Ar]3d5 4s1 Cr3+ : [Ar]3d3 4s0

Cr3+
3d 4s 4p

3d 4s 4p
[Mn(CN)6]3–
d2sp3 hy.
Magnetic Property : Paramagnetic
In this case(d3), no pairing is required as already two d orbitals are vacant.

IMPORTANT NOTE:
1. d1, d2, d3 configurations of metal ion does not involve pairing of electrons and hence we cannot call
these as LS complexes.

2. 3d7 metal ions(Co2+) mostly give outer orbital complex or High Spin complex(to be discussed after
this). However 4d7(Rh2+) and 5d7(Ir2+) metall ions can form LS complex with strong field ligands with
one pairing in (n-1) d orbitals and the other unpaired electron promoting to one vacant ns orbital.

3. d8, d9 and d10 always give Outer Oribital complex(sp3d2)

4. The details of all these and their cause will be explained in Crystal Field Theory.
(B)OUTER ORBITAL COMPLEX(OOC):
(i) Weak ligands form OOC.
(ii) Ligands having O- or halogen(X-) donors are weak.
Ex: H2O, Cl–, F–, Br–, I–, ox2–, OH– etc.
(iii) The inner (n–1)d orbitals remain in tact and hence the number of unpaired electrons remains
the same as the metal ion. Hence these complexes are called HIGH SPIN(HS) complexes or Spin Free
complexes.
(iv) In this case, 2 outer nd orbitals namely d x 2  y 2 and d z 2 alongwith with ns and np orbitals take
part in sp3d2 hybridization.

Example 1 : [FeF6]3– OS of Fe= +3

Fe(26): [Ar]3d6 4s2 Fe3+ : [Ar]3d5 4s0

Fe3+: 3d 4s 4p
4d

** ** ** ** ** **
FeF6] 3– 3d 4s 4p 4d
sp 3d2 hy. d
Magnetic Property: No. of unpaired electrons = 5
Magnetic Moment = 5(5  2)  35 BM

Example 2 : [Co(H2O)6]2+ :
Co(27) : [Ar] 3d7 4s2 Co2+ : [Ar] 3d7 4s0

Co2+: 4s
3d 4p 4d

** ** ** ** ** **
[Co(H2O)6] 2+
: 3d 4s 4p 4d
sp 3d2 hy.

Magnetic Property: No. of unpaired electrons = 3

SAQ: Draw the VBT diagram for the following complexes (i) [Ni(NH3)6]2+ (ii) [Co(en)3]3+
(iii) Fe(H2O)6]2+
 Tetrahedral(Td) Complexes(CN=4):
1. Weak Field ligands often form tetrahedral(Td) complex with 3d TM ions.
Ex: Ligands: Cl–, F–, H2O etc Metal ions of Co, Fe, Cu, Cr, Mn, Ni etc
2. Metal ions having d10 configurations (eg Zn2+, Cd2+, Hg2+, Cu+ etc) form Td complexes both
with weak field and strong field ligands.
3. The outer ns and np orbitals are used in sp3 hybridisation. Since the number of unpaired electrons
in the (n–1)d orbitals remain fixed, these complexes also called High Spin(HS) complexes under
CN=4 catetory.
4. [Ni(CO)4] forms Td complex despite CO being a strong field ligand. Interestingly it is a low
spin complex(diamagnetic) because ON of Ni =0. This anomalous behaviour of Ni(0) will be explained
later.

Example 1: [NiCl4]2– : OS of Ni = +2
Ni(28) : [Ar]3d8 4s2 Ni2+ : [Ar]3d8 4s0

Ni2+ : 3d 4s 4p

[NiCl4]2– 3d 4s 4p
sp3 hybridisation

y2 Magnetic Property: paramagnetic. No. of unpaired electrons = 2

Example 2 : [Ni(CO)4]: OS of Ni = 0
Ni(28) : [Ar]3d8 4s2

Ni0 :
3d 4s 4p

[Ni(CO)4]: 3d 4s 4p

sp3 hybridisation
The two electrons from 4s get transferred to 3d to make 5 pairs of electrons.
Magnetic Property: Diamagnetic

SAQ: Draw the VBT diagram for (a) [CoCl4]– (b) [Zn(CN)4]2–
Square Planar(SP) Complexes(CN=4):
1. Strong Field Ligands(Carbon and Nitrogen donors) usually form SP complexes.
2. Both strong and weak field ligands form SP complexes with 4d and 5d series of TM(heavier TM).
3. The metal uses one vacant (n–1)d orbital namely d x 2  y 2 to undergo dsp2 hybridisation. If that is
not present, the pairing of electrons takes place in the (n–1)d orbitals to make one d-orbital vacant. If
required an electron can jump over to one vacant np orbitals as only two p-orbitals namely px and py are
used in the hybridisation. Since the number of unpaired electrons get reduced in some cases, these are
sometimes called LS complexes under CN=4.

Example 1 : [Ni(CN)4]2– OS of Ni = +2

Ni2+ : [Ar] 3d84s0

3d 4s 4p

[Ni(CN)4]2– : 3d 4s 4p
dsp2 hybridisation

Magnetic Property: Diamagnatic

N.B: Pd2+ and Pt2+ will form SP complexes with both weak field ligands like Cl–, F– etc and also with
strong ligands like CN–, en, NH3 etc. Its cause will be known from Crystal Field Theory to be discussed
later.

Example 2 : [Cu(CN)4]2– :

Cu2+: [Ar]3d94s0
3d 4s 4p

3d 4s 4p
[Cu(CN)4]2–
dsp2 hybridisation

One electron from 3d jumps over to the vacant 4pz orbtal to make one 3d orbital free.

It is now believed that instead of dsp2, in this case sp2d hybridisation takes place. One outer nd
orbital is used in stead of inner d-orbital. The unpaired electron remains in tact in 3d orbital.

3d 4s 4p 4d
sp2d hybridisation
The reason for this belief is that Cu2+ is not readily oxidised to Cu3+. Had the electron been in 4p, which is more
energetic than 3d, the electron would have been lost easily to give +3 state. This does not happen. In stead
Cu3+ is a very strong OA. This proves that the unpaired electron remains in tact in 3d orbital and one outer 4d
vacant orbital is used for sp2d hybridisation.

SAQ: Draw the VBT diagram for the following. (i) [PdCl4]2–

SAQ: Indicate which of the following are Td and which SP complexes.

(a) [CuCl4]2– (b) [Ni(CO)4] (c) [Ni(CN)4]2– (d) [Zn(NH3)4]2+
(e) [CoF4]2– (f) [PtCl4]2– (g) [Pd(en)2]+ (h) [HgI4]2–

Merits of VBT:
1. It could explain the shapes of complexex.
2. It could explain the magnetic properites of most complexes.
Limitations of VBT:
1. No logic and explanation for HS(OOC) and LS(IOC) complexes.
2. Colour(spectroscopic) properties(optical spectra) of complexes cannot be explained by VBT.
3. Magnetic properties of many complexes could not be explained by VBT.
4. Stability of complexes and lowering of energy during complex formation could not be explained.
5. Why C- and N- donors are strong field ligands while O- and halogen donors are weak, could not
be explained.
6. Many complexes under CN=6 are distorted Octahedral geometry. This cannot be explained by
VBT.
7. Temperature depedence of magnetic property cannot be explained.
(B) CRYSTAL FIELD THEORY(CFT)
This theory has been advanced by Hans Bethe and John Hasbrouck van Vleck to win over the
limitations of the VBT to a large extent. But interestingly the assumptions in CFT is very ironical as it
contradicts VBT in the nature of bonding.
Assumptions:
(1)The bonding between the metal ion and the ligands is purely electrostatic(ionic). The ligands
are regarded as point charges(ionic ligands) or point dipoles(neutral ligands).
(2) The approach of ligands towards the metal ion with a defined geomtry brings about
breaking down the degnerary of the five (n–1) d-orbitals containing electrons in the metal ion. In other
words, the d-orbitals are split into different sets with an energy gap between them.

Conceptual Analysis:
1. The repulsion between the electron charge density of the ligands and the (n–1) d electrons of the
metal ion brings about increase in the energy of the system according to the potential energy equation.
qq '
Ek
r
Since transitional metals have smaller size than s-block elements and most importantly they have electrons
in the five d-orbitals which are virtually the valence electrons. These d-orbitals lack spherical symmetry.
The d-oribitals differently interact with the ligands’ electric field, thus breaking down the degeneracy.

2. Look to the irony. The same energy equation given before explains why there is strong metal-
ligand bonding? This is due to strong attraction between the +ve charge of the metal ion and the negatively
charged ligands. Small size and high +ve charge makes the bond for transition metal complexes stronger
and hence these metals are more prone to form complexes than other metals particularly s-block metals
like Na+ or K+ etc. having higher size and smaller charge.

3. CFT deals primarily with the splitting of d-oribitals due to repuslion as explained before and
quantitiatively explains the strengths of the ligands and metal ions, as we shall see later, though in most
cases, its cause cannot be explained. The electrons in the (n–1) d orbitals are redistributed in the split d-
oribitals following Hund’s rule and Paul’s exclusion principle. Aufbau principle is violated in in some
cases due to the complicating factor called Pairing Energy, as we shall see later.

(i) OCTAHEDRAL COMPLEXES:

In octahedral complex, we assume that the ligands approach
from the directions of three perpendicular axes. Had the negative
charge from six ligands are uniformly distributed over the surface
of an imagiary sphere around the metal ion, then all the five oribitals
still would have been degenerate but with enhanced energy. This is
called the hypothetical Barycentre. However, the six approaching
ligands along the axes intereact relatively more with the d-orbitals
whose lobes lie along the axes( d x 2  y 2 and d z 2 ) than those whose
lobes lie in between the axes ( d xy , d yz and d zx ). This is because in
the latter d-orbitals the lobes lie farther away from the approaching ligands. Thus there is a splitting of
the five d-oribitals into two sets, namely,
 (i) eg set : containing d x 2  y 2 and d z 2 orbitals
(ii) t2 g set : containing d xy , d yz and d zx orbitals
Due to relatively greater repulsion between ligands and eg set of oribitals, eg set has greater energy than
the t2g set. The energy gap between the two sets is called Octahedral Splitting(0). According to the
principle of conservation of energy, the three t2g set of orbitals lose as much energy as the two eg set of
3  3 
orbitals gain. That is why eg is set is 0 (0.60) above the hypothetical Bary Centre    0  or +0.60
5  5 
2  2 
and t2g set is  0 (0.40) below the Bary Centre    0  i.e –0.4 0. 0 sometimes called 10Dq, so
5  5 
that eg set is 6Dq above the Bary centre and t2g set is 4Dq below the Bary centre.

eg
3 
+ 5
0 +6 Dq
0 (10Dq)

Bary Centre 2
- 5 0 -4Dq
(hypothetical)

t2g

degenerate (n-1)d
orbitals of f ree
metal ion ( d -orbital splitting in an octahedral crystal filed )

N.B: Significance of the notations: The notations t2g and eg are derived from molecular symmetry.
e = doubly degenerate; t = triply degenerate
Dq = D for ‘d’ orbital and ‘q’ for quantum
g = gerade : having inversion centre(centre of symmetry)
t2 : two sets for t- under octahedral distortion(to be discussed later)

IMPORTANT NOTE: Though CFT does highligt on the splitting of d-orbitals, it is often silent about the net
energy change during the process. Since there are two opposing forces operating, one attraction which decreases
the net energy of the system leading to stable metal–ligand bonding and second the repulsion between (n–1) d
electrons and ligands which increases the energy of the system. The net result is decrease in energy. Hence the
energy level of two sets eg and t2g proportionately come down(not shown in the above diagram), without
altering 0 and gaps between each set with the barycentre). In all subsequent figures, we shall show the
splitting from the barycentre, ignoring the level of free metal ion for the sake of simplicity.
Low Spin(LS) and High Spin(HS) Complexes for d4 – d7 metal ions:

Electron Spin Pairing Energy or Pairing Energy(PE):

The energy required(increased) to bring about pairing of electrons in an orbital by overcoming
the force of repulsion is called PE. PE is nearly constant for a given metal which is independent of the
OS of the metal ion and nature of ligands with which it is bonded. 3d series metal ions have greater PE
than 4d/5d series metal ions as the latter d-orbitals are more diffused and hence the repulsion factor is
less.
There are two situations that arise here.

(a) Case-I: 0 > PE (Low Spin Complex)

If 0 is greater tha PE, then t2g set is completely filled(6 electrons) following Hund’s rule and
Pauli’s exculsion principle. Then the eg set gets filled following the above two rules. Due to pairing
electrons, the number of unpaired electrons gets reduced for metal ions having d4 – d7 configurations.
Hence such complexes are called Low Spin(LS) complexes.

(b) Case-II: 0 < PE (High Spin Complex)

On the other hand, if 0 is lesser tha PE, Aufbau principle is violated. Both the t2g and eg orbitals are
singly occupied then pairing begins from t2g set followed by eg set. In this case, the number of unpaired
electrons remain the same as the free metal ion, which is obviously more than LS complexes. Such
complexes are therefore called High Spin(HS) complexes. Electron distributions in LS and HS
complexes from d4–d7 metal ions are shown below.

d4 metal ion: (eg Cr2+, Mn3+) :

LS :
eg

0

( No. of Unpaired electrons = 2)

t2g

HS:

eg
0
( No. of Unpaired electrons = 4)

t2g
d5 metal ion: (eg Mn2+, Fe3+):
LS:
eg

0

( No. of Unpaired electrons = 1)

t2g

HS:

eg
0
( No. of Unpaired electrons = 5)
t2g

d6 metal ion: (eg Fe2+, Co3+):

LS:
eg

0

( No. of Unpaired electrons = 0)

t2g

HS:

eg
0
( No. of Unpaired electrons = 4)
t2g

d7 metal ion: (eg Co2+):

LS:

eg

0
( No. of Unpaired electrons = 1)

t2g

HS:

eg
0
( No. of Unpaired electrons = 2)
t2g
N.B: 1. d1 – d3 and d8–d10 metal ions have unique electronic distriutions irrespective of wheter 0 is
greater than PE or vice versa. So LS and HS terms are meaningless for such metal complexes.
2. LS complexes are equivalent to Inner Orbital Complexes and HS complexes are equivalent to Outer
Orbital Complexes as per VBT.

Whether 0 is greater than PE or the vice versa, we must know more about 0.

OCTAHEDRAL SPLITTING(0):

1. This is the energy gap between the two sets of d-orbitals. It is

often expressed in wave number units i.e cm–1( E  hc ) in stead of energy
unit.
2. It is experimentally determined from the UV-Visible absorption
spectrum of the complex. The wavelength ( max ) at maximum
1
intensity(Absorbance) of absortion gives the 0 value (   ).

Factors influencing 0 :
The folllowing three factors influence 0 value.
(a) Nature of Ligands

(b) Nature of metal ions ( 3d, 4d or 5d series)

(c) Oxidation State(OS) of the metal ion

N.B: In fact, the splitting of d-oribitals depends also on Coordination Number and geometry of the
complex. Here we look for octahedral complex(CN=6). In tetrahedral and square planar
complexes(CN=4), we shall see later that splitting will be different.

(1) Nature of Ligands:

Spectrochemical Series of Ligands:
Different ligands have different capabilities of splitting the d-oribitals. From a large number of
studies it is known that ligands can be arranged in an approximate sequence according to their ability to
cause d-orbital splitting. This series is known as the spectrochemical series.

Strong Field and Weak Field Ligands:

C– and N– donor ligands split to a greater extent in the order: C– donor > N– donor. O– and X–
(halogen) donor ligands split to a lesser extent in the order O– donors > X– donors. In other words, the
0 values for C– and N– donor ligands are greater than those of O– and X– donor ligands. The ligands
which splits the d-orbitals to a greater extent(greater) are called Strong Field Ligands. Carbon and
Nitrogen donors having multiple bonds(CO, CN–,NO2– etc) and Phosphorus donor(Ph3P) are Strong
Fileld Ligands. These are called -donor and -acceptor ligands, about which we shall discuss later.
Ligands which produce lower splitting are called Weak Field Ligands. O– and X- donors are Weak
Field Ligands. Other N– donors like NH3, en etc having a lone pair on N atom have intermediate
strength and for most purposes are regarded as Strong Field ligands. The reason for the order of ligands
can be explained by using another theory of Metal-Ligand bonding called Ligand Field theory which
makes use of MOT blended to CFT. CFT cannot explain the cause of the order in spectrochemical
series. CFT cannot explain why O– and X– donors are Weak Field Ligands, why among the halides, F– is the
strongest and I– the weakest. Why ligands like CO, CN–, PPh3, NO2– are strong filed ligands, H2O, NH3, Py
are ligands with intermediate splitting ability etc, cannot be known now from CFT. From CFT the order is
determined experimentally by selecting a fixed metal ion with fixed OS and varying the ligands to form complexes
and from their uv-visibile absorption spectra, we can know the 0 values and hence form spectrochemical
series.

Series:
O22– < I– < Br– < S2– < SCN– (sulphur bonded)< Cl– < NO3– < N3– < F– < OCN–(O-
bonded) < OH– < ONO– < C2O42- < O2– < H2O
< NCS– (N-bonded) < EDTA 4– < NH3 Py < en < bipy < phen < NO2– < PPh3 <
CN– < CO

Upto H2O, the ligands usually behave as Weak Field Ligands and beyond H2O as Strong Field
Ligands. Strong Field Ligands form LS complexes as 0 is greater than PE while Weak Field Ligands
form HS complexes as 0 is less than PE. This is an approximate thumb rule because 0 further depends
on nature of metal ion and its OS. The border line ligands from H2O to NH3 can on some cases act
differently. H2O can form LS complexes with strong field metal ions(we shall see later) while NH3 can
form HS complex with weak field metal ions(we shall see later).

(2) Nature of Metal ion:

The splitting increases as we go down a TM group in the order (keeping OS fixed)
3d metal ion <<< 4d metel ion  5d metal ion
eg : Co << Rh2+ Ir2+
2+
Fe3+ << Ru3+  Os3+
3+ –1 ;
[Co(NH3)6] 0 = 22900 cm
3+
[Rh(NH3)6] 0 = 34000 cm–1
3+
[Ir(NH3)6] 0 = 40000 cm–1

4d and 5d metal ions are regarded as Strong Field Metal ions as they produce larger splitting than 3d
metal ions. With intermediate field ligands like H2O, they produce larger splitting and form LS complexes.
4d and 5d orbitals have greater size than 3d orbitals and therefore the effectiveness of overlap between
the ligand oribitals with the 4d/5d orbitals is more(talking in the language of Ligand field theory) and
hence cause greater splitting. Due to lanthanide contraction the sizes of 4d and 5d TM are nearly same
along a group and hence the difference between 4d and 5d metal ions is not much.

(3) OS of metal ion:

The splitting increases with increase in OS of the metal ion. This is because, as the magnitude
of +ve charge increases, size of the TM ion decreases and +ve charge density increases. There is a
greater attraction and the ligands come nearer to the metal ion. Hence the repulsive interaction factor
becomes greater so as to split more.
Co2+ < Co3+; Mn2+ < Mn3+ < Mn4+ and so on

[Co(H2O)6]2+ : 0= 9300 cm–1; [Co(H2O)6]3+ 0 = 18600 cm–1

4– –1
[Fe(CN)6] : 0= 32800 cm ; [Fe(CN)6]3– 0 = 35000 cm–1 .
2+ –1
[V(H2O)6] : 0= 11800 cm ; [V(H2O)6]3+ : 0= 17850 cm–1;
You find in this case, the ligand remaining same(H2O), the first complex i.e[Co(H2O)6]2+ is HS while the
second i.e [Co(H2O)6]3+ is LS as PE is usually less than 18000 cm–1 but greater than 9300 cm–1 for most
metals. Since H2O has intermediate splitting ability, change in the metal ion and its OS can change the
nature of complex from LS to HS or vice versa.
Spectrochemical Series of Metal ions:

A few metal ions have been arranged in the increasing order of their splitting ability. That series
is a short one and called spectrochemical series of the metals. This order is largely independent of the
nature of metal ion. The first few metal ions are Weak Field Ligands, as they produce smaller splitting.

Mn2+ < Ni2+ < Co2+ < Fe2+ < V2+ < Fe3+ < Cr3+ < V3+ < Co3+ < Rh2+ < Mn4+ < Mo3+ < Rh3+ < Ir3+ < Re3+ < Pt4+.

N.B: 1. Since Mn2+ and Co2+ are in the first part of the series i.e they are weak field metal ions, they
form HS complexes with ligands like NH3 which have intermediate splitting ability.

Examples:
1. [Co(en)3]3+ : LS complex
It is a LS complex as Co3+ is a strong field metal ion and en is a intermediate field ligand.
Although we do not have 0 and PE data to compare, one can predict with confidence that it is ought to
be LS complex. (0 > PE)
Co3+ : 3d6
eg

[Co(en)3]3+ Barycentre
(Diamagnetic)
t2g
4–
2. [CoF6] : HS complex
As F– is a weak field ligand. PE is greater than 0 , irrespective of whether it is Co2+ (as this case)
3+
or Co .
Co2+ : 3d7

eg

[CoF6]4– : (Paramagnetic(same as free metal ion)

Barycentre
t2g

SAQ 0 and PE energy data are given for the following two complexes.
(a) [CoF6]3- : 0 =13000 cm–1 and PE = 21000 cm–1
(b) [Co(NH3)6]3+ : =23000 cm–1, PE = 21000 cm–1
Predict what type of complex each will form, ie LS or HS ? Show with CFT diagram.
Solution:
(a) HS complex : [CoF6]3- : Co3+ : 3d6 (0 < PE)

eg

Barycentre
t2g
3+ 6
(b) LS complex : [Co(NH3)6] : 3d (0 > PE)
eg

Barycentre
t2g
Unique configurations for d1– d3 and d8 – d10:

Whether 0> PE or 0 < PE, the above metal ions have unique d- level configurations. So
magentic properties will remain unchanged. So it is not worthwhile to use the terms LS and HS octahedral
complexes to such metal ion comlplexes. Of course higher and lower 0 values will affect their optical
spectra and hence colour properties which we shall discuss later.

d1 : Ti3+ complexes
eg

t2g

d2 : V3+ or Ti2+ complexes

eg

t2g

3 3+
d : Cr complexes
eg

t2g

d8 : Ni2+ complexes

eg

t2g

d9 : Cu2+ complexes

eg

t2g

d10 : Zn2+, Cd2+, Hg2+ complexes

eg

t2g
SAQ: Predict whether the complex will be LS or HS ? 0 and PE values are not given. You should have to
make a logical guess with your knowledge about the factors affecting Oh splitting. Draw their splitting diagram.
(a) [CoF6]3– (b) [Rh(CO)5Cl]2+ (c) [Fe(py)6]2+ (d) [Fe(H2O)6]2+
3– 3+ 4–
(e) [FeBr6] (f) [Co(NH3)6] (g) [Mn(CN)6]
–
Solution: (a) HS : as F is a Weak Field Ligand
(b) LS : as Rh3+ is a strong field metal ion, also CO is strong field ligand
(c) LS: Py is a intermediate field ligand(can be taken as strong field ligand) while Fe2+ is not
very weak field metal ion like Mn2+, Ni2+ etc. so possibility of forming LS complex is more. Go for LS.
(d) HS : H2O is weak(intermediate) field ligand, so possibility of forming HS is high. Go for HS.
(e) HS : Br– is Weak field ligand (f) LS :Co3+ is a strong field metal ion and NH3 is fairly
strong field ligand.
(g) LS : CN– is a strong field ligand although Mn2+ is weak field metal ion.

(ii) Tetrahedral Complexes : (CN = 4) :

The general observation is that under CN=4, weak field ligands with weak field metal ions of
3d series form tetrahedral complexes, not square planar complexes, although a few exceptions do
exist. As we shall see later square planar geometry comes as an extreme case of tetragonal distortion
of octahedral crystal field, which necessitates much greater splitting. Hence strong field ligands or
strong field metal ions or both form square planar complex.

In tetrahedral geometry, the ligands do not approach along direction of the axes unlike the
case in octahedral geometry. We can visualise this by considering the approach of
z
ligands from the opposite corners of the two opposite faces of a cube towards
centre where metal ion is located. The perpendicular axes passing through the metal L
ion lies inside the cube . The three d-oribtals namely d xy , d yz and d zx (t2 set) are L
n+
M x
relatively closer(though not along) to the direction of the approaching ligand orbitals
L
than the other two d-orbitals namely d x 2  y 2 and d z 2 (e set) Thus there will be splitting L
y

of d-oribtals in the opposite manner as compared to octahedral splitting. With

respect to hypothetical barycentre, the former group of orbitals called t2 set acquires higher energy and the
latter group of orbitals called e - set acquires lower energy. The gap between them is called Tetrahedral
Splitting(t).

(Tetrahedral appproach of ligands)

2 t2
+ t
5

t
Barycentre 3 (Tetrahedral Splitting)
- t
5
e
t is nearly half 0 with same metal ion and same ligands.
4
t 
0
9
The reason for this is twofold.
 (1) The ligands are not approaching along the direction of d-orbital axes and
hence the repulsion factor is less and hence relative splitting is also less.
(2) In tetrahedral field there are four ligands as against six ligands in octahedral
field, for which the efficacy of splitting is less in case of the former.
N.B: The subscript ‘g’ (t2g and eg) is not used here as there is no inversion centre in this Td geometry.

For most cases t < PE, hence tetrahedral complexes are always HS complexes and the number of
unpaired electrons in the complex remains same as the free metal ion. The e-set and t2 sets are singly
occupied then pairing starts from e set

Example: [MnCl4]2–:
Mn2+ : 3d5

t2

e
SAQ: A Td complex absorbs at 545 nm. What would be octahedral splitting with same metal ion and
ligands ?
Solution:
hc 6.627 1034 Js  3 108 ms 1
t   9
 3.65 1019 J
 545 10 m
9
0    t  8.3  1018 J
4
This energy is per molecule for one electron transition from lower d-set to higher d-set. If we want to
find the energy per mole then we have to multiply with above answers with Avogadro’s number.

(iii) SQUARE PLANAR COMPLEXES (CN = 4)

Square planar geometry is visualised as the extreme case of distortion in octahedral geometry.
When two trans ligands on the z-axis in an octahedral field are slowly stretched out going farther away
from the metal ion in the z-axis, distortion (called z-out distortion) in Oh field occurs. We shall see later
that there are many Oh complexes which have distorted Oh geometry in stead of a regular Oh one. This
distortion results in further splitting in the t2g and eg set of orbitals. The d-oribitals which have a z-
components like d z 2 orbital in the eg set and d yz & d zx orbitals in the t2g set acquires relatively lower
energy than the other orbital in their respective sets. This is because, these orbitals are either lying along
z-axis or closer to z-axis and the two ligands are also stretched out along z-axis. Hence the decrease in
repulsion will be more pronounced in these oribitals than those which do not have a z-component like
d x 2  y 2 orbital in e and d xy orbital in t set. Hence d-orbitals carrying z-component will possess lower
g 2g
energy(go down) than their other parter( which go up). Thus further splitting occurs.
As the z-out distortion is continued, the gaps between the two pairs of sets further increase. If
you imagine that the two trans ligands are completely removed as an extreme situation, then Oh
geometry is converted to square planar(SP) geometry and at that situtation, the d z 2 orbital lies
below d xy orbital. This results in the splitting diagram of SP complex.
 d 2 2
x -y

0
d 2 2
x -y

eg
d z2 dxy
0
0.656 0
Barycentre dxy

d
t2g z2
0.0860
Oh dyz , dzx
s plitting Distorted dyz dzx
Oh ,

s quare planar

Square Planar CFT splitting consists of three energy terms. The net square planar splitting will be the
sum of the three energy gaps. The uppermost gap between d x 2  y 2 and d xy is the largest one which is
nearly equal to octahedral splitting( 0).
 SP   0  0.656 0  0.086 0  1.742 0

PE is greater than the two lower energy gaps but smaller than 0 (the uppermost gap). So while
redistributing electrons, all the three lower level sets(4 orbitals) are singly occupied first and then
pairing starts from the lowermost set, leaving the uppermost orbital i.e d x 2  y 2 vacant until the 9th
electron comes in metal ions like Cu2+ .

Mostly d8 metal ions like Ni2+(with strong field ligands) and Pd2+ and Pt2+, Ag3+, Cu3+, Au3+(with both
strong and weak field ligands) form SP complexes. All these complexes are diamagnetic.

Ex. [Ni(CN)4]2–: 3d8 :

d x2- y2

dxy
barycentre
dz 2

dyz ,dzx
SP splitting

The complex is diamagnetic.

Crystal Field Stabilisatiaon Energy(CFSE):
With respect to the barycentre, what net energy is lost during complex formation is called CFSE. The
more energy lost means more is the stability of the complex. CFSE is always negative or at the most
zero.
CFSE depends on the following factors.
(a) Geometry of the complex (b) No. of d-electrons in metal ion
(c) Spin Pairing Energy(PE) (d) Nature of Ligands (Splitting values)

CFSE = Eligand field – Eisotropic field

Where Eligand field = Total energy in the complex in the filled d-oribitals after splitting
Eisotropic field = Total energy in the free metal ion

(A) Octahedral Complex:

3 2
Eligand field = + 0 × neg – 0 × nt2 g + m × P
5 5
Where neg = number of electrons in the eg set, nt2 g = number of electrons in the t2g set
m = the number of electron pairs; P = Pairing Energy(PE)
Note that energy increases due to presence of electron in the eg set and when electron is pushed in an
orbital for pairing. On the other hand, energy is lowered when electrons occupy the t2g set.
Eisotropic field = z × P
Where z = number of electron pairs in the degenerate d-orbitals of the free metal ion.
The net energy is either lost(–ve) or becomes zero. If CFSE values comes +ve, then such complex is
unstable.

Unique d-configuration: d1 – d3 and d8 – d10 (No HS or LS concept in these cases)

CFSE values:
2 4 6
d1 :   0 d2 :   0 d3 :   0
5 5 5
 12 6  6  12 9  3
d8 :    0   0  3P   3P     0 d9 :    0   0  4 P   4 P     0
 5 5  5  5 5  5

 12 12 
d10:    0   0  5P   5P   0
 5 5 
HS and LS complexes from d4 – d7 :
 6 3  3  8  8
d4: HS:    0   0  0  0    0 LS:    0  P   0    0  P
 5 5  5  5  5

 6 6   10 
d5: HS:    0   0   0  0 LS:    0  2 P   0  2 0  2 P
 5 5   5 
 8 6  2  12  12
d6: HS:    0   0  P   P    0 LS:    0  3P   P    0  2 P
 5 5  5  5  5
  10 6  4  12 3  9
d7: HS:    0   0  2 P   2 P    0 LS:    0   0  3P   2 P    0  P
 5 5  5  5 5  5
In all the HS complexes from d4 – d7 and the unique cofigurations of d1 – d3 and d8–d10, the CFSE shows
a typical trend as shown below. CFSE values have not ‘P’ term in them. d0, d5(HS) and d10 configurations
have zero CFSE values. Others have –ve CFSE values.
0 d5 d10
0 d

(Only HS and unique configurations)

d3 d8
(B) Tetrahedral Complexes :
2 3
Eligand field = + t × nt2 g – t × neg + m × P
5 5
Eisotropic field = m × P

Since tetrahedral complexes are always HS, the ‘P’ terms cancel out and CFSE does not carry ‘P’ term.

3 6 6 2 4
d1:   t d2 :   t d3 :   t   t    t
5 5 5 5 5
6 4 2 6 6 9 6 3
d4:  t   t   t d5:   t  t  0 d6:  t  t   t
5 5 5 5 5 5 5 5
12 6 6 12 8 4 12 10 2
d7 :  t  t    t d8 :  t  t   t d9:  t   t    t
5 5 5 5 5 5 5 5 5
12 12
d10 =  t  t  0
5 5
In Td complex, we find a similar trend of variation of CFSE as we found in the HS and other unique d-
configurations of octahedral complexes.
0 d5 d10
0 d

d2 d7
(C) Square Planar Complex:
The following splitting diagram is to be used to find the
CFSE in SP complexes. With respect to the barycentre,
the energy values are shown in respect of each level with
+ve and –ve signs. In the earlier splitting diagram, we
showed only the gaps between the levels.
[Ni(CN)4]2–:
d8 :

d x2- y2

dxy
barycentre
\ dz 2

dyz ,dzx
SP splitting

CFSE=  0.51 0  4  0.430  2  0.23 0  2  4 P   3P  2.44 0  P

SAQ: Calculate the CFSE of [Co(NH3)6]2+, 0 = 30,000 cm–1, PE= 17000 cm–1.
Solution: Co2+ : 3d7 . As 0 > PE, it is a LS complex.

eg

0

t2g

 12 3  9
CFSE =   5 0  5 0  3P  2 P   5  0  P = –37000 cm–1.
 

Colour Properties in Complexes:

Most of transitional metal complexes and their compounds are differently coloured in aqueous
solution. This colour is due to two possibilities.
(a) d - d transition
(b) Charge Transfer Spectra(CTS) or Charge Transfer Complex(CTC).
(A) d – d transition:
* This is explained by the CFT’s splitting of d-orbitals. If there is at least one vacancy in
the upper set of d-orbitals(eg or t2g for Oh and Td complexes respectively), then one electron transits
from the lower set to higher set by absorbing a quantum of energy in the visible region and the colour
that we see is its complimentary colour.
Octahderal complex: [Fe(CN)6]4– : Yelllow Fe2+ : 3d6. Transition from t2g to eg occurs.

d-d transition
0

h

The due d–d transition, the complex absorbs energy from violet region and the complex looks yellow as
the complimentary colour of violet is yellow.
Tetrahedral Complex: [CoCl4]2–. blue: Co2+ : 3d7 : Here d-d transition occurs from e set to t2 set.

t2

d-d transi ti on t d-d transiti on

h
e

The complex absorbs in the organge region and looks blue.

Square Planar Complex:
[Cu(NH3)4]2+: Ink Blue. Here the d-d transition occurs from dxy to d x 2  y 2 .

d x2-y2 d x2-y2
o
h
dxy dxy

d z2 d z2

dyz , d zx dyz , d zx

The complex absorbs in the organg-yellow region and appears ink blue.

* d0 and d10 metal complexes are usually colourless as d – d transition is not possible.
Examples: [Ti(H2O)6]4+ : Colourless (d0); [Ti(H2O)6]3+ : purple (d1)
[Cu(NH3)4]2+ : Ink blue(d9) [Cu(CN)4]3– : Colourless (d0)
The d metal complexes which are colourless are Sc , Ti4+, V5+etc. The d10 metal ion complexes which
0 3+

are colourless are Cu+, Ag+, Au+, Zn2+, Cd2+, Hg2+ etc.
* The complex which completely absorbs in the UV region does not have colour in the visible
region and hence look colourless. Although absorption does occur, which is known from UV-visible
spectrum of the complex, the complex is colourless. Example [Cu(CN)4]2– (d9).
* Many cyanide complexes have light yellow in colour because, they absorb in the UV region
mostly but the tail of the absorption peak penetrates into a initial part of violet region. Hence the
complex looks light yellow. Example: [Co(CN)6]3–. We shall see later that the colour is mostly due to
Charge Transfer spectra(not d-d transition) for cyanide complexes.
Prediction of colour of Complex from Colour Wheel:
Substractive colour mixing concept is used to predict the expected colour of the complex. For
that the following colour wheel can be used. The colour wheel is prepared by taking six colours(ignoring
the indigo) and writing in correct sequence of increasing wavelength().

O 580
650

R Y
750
400 560

V G

B 490
430

Divisions are made by drawing one horizonatal line in the circle(colour wheel) and then drawing
a cross mark as shown. Starting from violet from left, mark the other colours in anticlockwise manner
in the sequence V - B - G - Y - O - R. The successive gaps between the colours starting from 400 nm is
as follows.
30 – 60 – 70 – 20 – 70 – 100
That means : Violet : 400 nm – 430 nm : Blue : 430 – 490 nm : ; Green : 490 – 560 nm
Yellow : 560 – 580 nm ; Orange : 580 – 650 nm; Red : 650 – 750 nm

N.B: Pink colour is equivalent to Red (Red+whilte) and Purple colour is equivalent to violet(Red+Blue).
The complimentary colours remain opposite to each other in the wheel. If certain complex absorbs blue
it will look orange. If it absorbs red it will look green and so on.
* Low Spin(LS) complexes contains strong field ligands (C and N donors) and absorbs in
higher energy(lower wavelength) in the V – B – G region and therefore appear opposite i.e Y – O – R.
* High Spin(HS) complexes contain weak field ligands (X, O donors) which absorb at lower
energy(higher wavelength) in the R – O – Y region and hence appear G – B – V.
SAQ: An octahedral complex of 3d6, appears yellow. What colour does it absorb. It is a LS or HS
complex ?
Solution: It absorbs violet( strong field ligand) and hence appear yellow. So it must be a LS complex.
SAQ: An octahedral complex absorbs at max = 535 nm. Find o and which colour it will exhibit ?
Solution: 535 nm = green. If it absorbs green colour light then it will appear red.
hc 6.627 10 34 Js  3 108 ms 1
o    3.716 1019 J
 535 109 m
SAQ: Out of two Co3+ complexes with Cl– and NH3 ligands, one appears orange and the other bule.
Preduct which is which ?
Solution: Since Cl– is a weak ligand, will absorb at higher wavelength orange region and appears blue
while NH3 being strong ligand and will absorb in the blue region and appears orange.
SAQ: The absorption maximum(max) values of of few complexes are given. Predict their colours.
(a) [CoF6]3– : max=700 nm (b) [Co(NH3)5Cl]2+ : max=535 nm
(c) (Co(H2O)6]3+ : max= 600 nm (d) [Co(NH3)6)]3+ : max=475 nm
3–
(e) [Co(CN)6] : max=310 nm(UV) with its tail in violet region
Solution: (a) absorbs red, appears green (b) absorbs green, appears red
(c) absorbs organe, appears blue (d) absorbs blue, appears orange
(e) since tail of the absorption peak falls in the violet region, it will appear light yellow
SAQ: Certain complex give o = 3.75 × 10–19 J. What colour does it exhibit ?
Solution:
hc 6.627 1034  3 108
0  3.75 1019  
 
9
   530 10 m  530nm
It absorbs green light and appears red.

(B) Charge Transfer Spectra(CTS) or Charge Transfer Complexes(CTC):

Many TM oxo ions like MnO4–(purple) CrO42– (yellow) Cr2O72–(orange) , VO2+ (purple) etc. are coloured
although in all cases the TM has d0 configuration. The colour property is not due to d – d transition.
It is due to CTS. One electron from the Ligand transits to one empty orbital of the metal ion or vice
versa. During the transition, some colour is absorbed and its complimentary colour is observed. This is
a p – d transition or d – p transition which is highly allowed(see later). The colour intensity in CTS is
the highest, higher than complexes.
There are two types of CTS.
(a) LMCT : Ligand to Metal Charge Transfer: Most of the oxoions of the TM as cited above
are coloured due to this. Electron from ligand( or n)is transferred to the vacant orbital(eg or t2g) of
the metal ion. It is mostly a p – d transition. Many other TM compounds lke Fe(SCN)3 (blood red),
CdS(yellow), HgS(black), FeO(green), Fe2O3(reddish brown), TiBr4(orange), TiI4(dark brown) belong
to this category. In this case the metal ion gets reduced.
(b) MLCT: Metal to Ligand Charge Transfer : In this case, one electron from the t2g or eg set is
transferred * or * orbital of the ligand. Complexes having low OS of the metal sometimes show this
spectra. In this case the metal gets oxidised.
Examples: (a) [Ru(bpy)3]Cl2 (d6), [Cu(phen)2]Cl (d10)
(b) Complexes containing -donor and -acceptor ligands like CO, CN– show colour
primarily due to CTS. But they produce both LMCT as well as MLCT spectra. Hence it is difficult to
distinguish between them. Most complexes of these ligands are colourless as the absorption falls entirley
in the UV region. But in some cases, the tail of the peak extends to the violet region and hence appear
light yellow. Note that the weak d-d transition also occurs in this case, but its peak is buried inside the
intense CTS and not detected. Later we shall discuss more about the bonding in such ligands.

_________________________________________________________________________________
More about Colour Intensity:
I0
Absorbance: (Beer and Lambert Law) : A  log  cl
I
This gives the maximum intensity of absorption(Absorbance) in the UV-Visible spectrum of a compound.
Where A= Absorbance(Intensity of absorption); I0 = Intensity of incident light
I = intensity of transmitted light;  = molar extinction coefficent(absorptivity) : a constant
c = concentration of the solution, l = length of the spectrometer tube carrying the solution

Laporte Selection Rule(Orbital Rule) : The allowed electronic transition is when l = 1 . l = 0 is

forbidden transition.
That means d – d or p – p transition is forbidden. In stead d – p , p – d , s – p or s – d transition are allowed.
But in complex, we have d – d transition. More strictly this rule is valid when there is an inversion centre ‘i’in the
molecule like in Oh and SP geometry. In Td geometry, d – d transition is partially allowed.
Spin Selection Rule: s = 0 is allowed transition. That means S  0 is forbidden.

Breakdown or Relaxation of Selection Rule: Forbidden transition becomes partially allowed with
lower intensity of absorption due to the following reasons.
(a) Vibronic coupling: Due to asymmetric stretching vibration, centre of symmetry is lost and
Laporte selection rule is partially broken down.
(b) Mixing of Orbitals: In complexes, there is huge d - p mixing of orbitals. So Laporte selection
rule is partially broken down. d - d transition is partially allowed.
(c) Spin-Oribt coupling : Spin couples with orbital angular momentum(common in heavier TM
and Ln, An), so breakdown of spin selection rule occurs.

Intensity of Colour:
(1) Td complexes are relatively more intense than Oh complexes as there is no ‘i’ in the former
and the transition is partially Laporte allowed.
[CoCl4]2– : Intense blue colur (It is also spin allowed.) (  = 50 – 150)
(2) Oh and SP complexes have low intensity colour as there is ‘i’. But the transition is partially Laporte
allowed due to break down of selection rule.
Ex: [Mn(H2O)6]2+ (d5): pale violet: spin forbidden, but partially allowed due to spin-orbit mixing.
Laporte forbidden. ( = 0 – 0.1 )
2+ 7
Ex: [Co(H2O)6] : d : pale pink ( = 1 – 10 ). Little more intense than the previous case.
It is spin allowed. Though Laporte forbidden, but partially allowed due to breakdown of the rule.
(3) CTS/CTC producing species give most intense band ( = 1000 – 106). From intensity of the
uv/visible spectrum, one can know whether it is due to CTS or d–d transion. The high intensity of CTS
is due to Laporte allowed (p -d or d -p) and spin allowed nature of transition.

Intervalence Valence Charge Transfer(IVCT)

Compounds like Prussian Blue i.e Fe4[Fe(CN)6]3 Turnbull’s bule ie Fe3[Fe(CN)6]2 etc , the blue is due to
electron transfer from Fe2+ to Fe3+.
_________________________________________________________________________________
Drawbacks of Crystal Field Theory:
1. Covalent nature and hence shape cannot be explained.
2. -bonding is not considered
3. Cause of splitting power of many ligands could not be explained.
4. s and p-orbitals are considered in bonding.
5. Colour in d0 and d10 complexes cannot be explained.
 Stability of Complexes:
The common understanding about stability of a compound is its relative time period of existence without
breaking down or transforming to other substances. In this case, it is nothing of that sort. For complexes
there are two types of stabilities suggested by the pioneers.
(a) Thermodyanamic Stability : More the formation constant(equilibrium
constant) of complex, more is its thermodynamic stability. This is determined from the free energy
change of the complex formation reaction(G).
(b) Kinetic Stability: More the rate of reaction(reactivity) with which a complex
reacts, less is its kinetic stability. Such complexes are called LABILE complexes. Commonly, ligand
exchange reactions are considered for studying kinetic stability. If a complex reacts slowly, then it is
kinetically a more stable complex. Such complexes are called INTERT complexes. The reactivity is
determined from the energy of activation(EA) of the reaction.

Usually a thermodynamically stable complex is inert(kinetically stable) and a thermodynamically

unstable complex is labile(kinetically unstable). This means two stabilities go parallel. But in many
cases the two do not go hand in hand. This means that a thermodynamically stable complex can be
extremely labile and an unstable complex can be extremely intert. If the metal – ligand bond is strong
and G is more negative, then its formation constant(Keq) is large(high thermodyanic stability). It can
therefore be presumed that such bond cannot be easily broken (i.e the activation energy would be high)
and replaced by other ligands. Although this is true in several cases, but exceptions do exist. See these
examples.
Examples:
1. Hg2+ + 4 CN– [Hg(CN)4]2– KF = 1042 (formation constant)
[Hg(CN)4]2– + 4 14CN  [ Hg (14CN )4 ]2 k=rate constant is also high
A thermodynamically very stable complex(high KF) is simultaneously very reactive(Labile) to a particular
ligand substitution reaction with isotopically labelled cyanide ion.
2. [Cu(NH3)6]2+ is extremely unstable(low KF value) but it is also extremely inert(low
rate costant(k) for ligand substitution reaction.
3.[Fe(H2O)5F]2+ is thermodynamically stable(high KF value), but it is extremely labile(high
rate constant)
4. [Co(NH3)6]3+(aq) + 6H3O+(aq) [Co(H2O)6]3+(aq) + 6NH4+(aq),
This reaction has KF equal to 1064, which means backward reaction very less favourable. That means
[Co(NH3)6]3+is a thermodynamically unstable complex. But the above reaction takes place very slowly.
It takes several weeks for the reaction to complete. So it is an inert complex.
[Co(NH3)6]2+(aq) + 6H3O+(aq) [Co(H2O)6]2+(aq) + 6NH4+(aq)
For this reaction, the KF is equally high, meaning thereby that [Co(NH3)6]2+ is thermodynamically unstable
like Co3+ complex, but the above reaction occurs very fast, and completes in few seconds. Thus it is a
labile complex.
N.B: Thus the lability is mostly dependent on the metal ion and its oxidation state, not much on the
ligands.
So many anomalies do exist. Therefore we are inclined to believe that there is no fixed
correlation between the two stabilities. While one deals with G , the other with EA.
But in a general sense, stability of complexes usually refers to its theormodynamic stability.
Formation Constant(KF):

M+ L k1
[ML1]
k2 [ML2]
[ML1] + L

kn (The charges of metal ion and ligands not shown)

[MLn-1 ] + L [MLn ]

Kf
M + nL [MLn ]

k1, k2....., kn are called Stepwise formation constant. KF () is called the Overall Equilibrium Constant
or Formation consant or Stability constant.
KF () = k1 × k2 × ....... × kn

More correctly the steps should be ligand displacement reactions with aqua ligands, as in aqueous
solution all TM ions exist as aqua complexes.

2+ 2+
[Cu(H2O)4] + NH3 [Cu(H2O)3(NH3)] + H2O log k1 = 4.22

2+ 2+
[Cu(H2O)3(NH3] + NH3 [Cu(H2 O)2 (NH3)2 ] + H2O logk2 = 3.50
2+ 2+
[Cu(H2 O)2 (NH3 )2] + NH3 [Cu(H2 O)(NH3 )3] + H2 O logk3 = 2.92
2+ 2+
[Cu(NH3)4 ] + H2O logk4 = 2.18
[Cu(H2 O)(NH3)3 ] + NH3

We found that the stepwise formation constant decreases as we go to higher orders of substitution.
k1 > k2 > ....... > kn

This is because, as more ligands substitute H2O ligands, the number of H2O ligands becomes less and
hence the probability of substitution becomes less. Moreover, the steric crowding effect also is partly
resonsible for this decrease.
Instability Constant or Dissociation constant(KD) :
The equilibrium constant for the reverse reaction of formation of complex is called Instsability constant
or Dissociation constant, KD. KD is the reciprocal of KF.

K
M + nL f [MLn]
1
KD 
KD KF
[MLn ] M + nL
Factors Affecting Stability of Complexes:
1. Size and Charge of of the Metal Ion:
Smaller the size and greater the charge of the metal ion, greater is the charge density
(q/d) and hence greater is the metal-ligand bonding. Due to that the 0 and hence CFSE is also greater.
So stability is greater.
Ch arg e
stability 
size
[Fe(CN)6]3– >>> [Fe(CN)6]4– [Be(OH)4]2– >>> [Mg(OH)4]2–
KF 1031 108 107 120

Irving William Natural Order for M2+ Octahedral

HS complexes:
In a d-series, the size decreases among M2+ ions, so it is
expected that the stability of complexes should increase
among the HS complexes. But two anomaly occurs at Cr2+
and Cu2+ which appears as two humps. This is due to unusual
increase in CFSE in case of these two metal ions for Jahn
Tellar effect, which we shall discuss a little later.
Ti2+ < V2+ < Cr2+ > Mn2+ < Fe2+ < Co2+ < Ni2+ < Cu2+ > Zn2+

Zn2+ complex has less stability than Ni2+. Sc does not have a
2+ state. Ti2+ complex is least stable Cu2+ complex is most
stable due distortion in Oh geometry(we shall see later). Cr2+
complex is more satable than both V2+ as well as Mn2+, as it shows small Oh distortion.

(2) Nature of Metal ion:

Metal’s ability to split d-orbitals increases down the group(already discussed before). More the
splitting more is the CFSE and hence stability. The OS and the ligands to be kept fixed.
3d < 4d < 5d (metal ion stability order)
Example: [Co(H2O)6]3+ < [Rh(H2O)6]3+ < [Ir(H2O)6]3+
(3) Nature of Ligands:
More the strength of the ligand for splitting(spectrochemical series) of the ligand, more is the
stability of the complex. For this the metal ion and its OS to remain fixed.
Example: [CuF4]2– > [CuI4]2–
(4) Base strength of ligands:
More is the base strength of a ligand, stronger is the metal–ligand bonding and hence more is
the stability. Usually stronger bases are strong field ligands in the spectrochemical series. But base
strength is not the only criterion used to order the ligands in the spectrochemical series.
Example: [Cu(CN)4]2– > (Cu(NH3)4]2+ > [Cu(H2O)4]2+
as base strength order : CN– > NH3 > H2O
(5) Hard and Soft Acid - Base Theory(HSAB):
First row transition metal ions(3d series) which are hard acids form more stable complex with
small size ligands belonging to 2nd period like F–, H2O, OH–, NH3 etc, which are hard bases. Similarly
2nd and 3rd row transition metal ions(4d and 5d series), which are soft acids form more stable complex
with large size ligands belonging to 3rd and 4th periods like (Cl–, Br– , I–), which are soft bases.
Examples: [FeF6]4– > [FeCl6]4–; [PtF6]2– < [PtCl6]2–
[Ni(NH3)4]2+ > [Ni(PH3)4]2+ [Pd(NH3)4]2+ < [Pd(PH3)4]2+

(6) Chelate Effect:

Polydentate ligands form cyclic complexes which are called chelate complexes and hence the
such ligands are called chelating agents or ligands. Chelate complexes are significantly much more
stable than complexes having chemically similar monodentate ligands. See this example.
[Ni(H2O)6]2+ + 6NH3 [Ni(NH3)6]2+ + 6H2O KF = 4.0 × 108
[Ni(H2O)6]2+ + 3 en [Ni(en)3]2+ + 6H2O KF = 2.0 × 1018
The en complex is about 1010 times more stable than ammine complex despite having same donor
atoms. This extra stability in chelate complexes is called Chelate Effect.
A five membered cyclic complex with ligands like en is more stable than a six mebered cylcic
complex with ligands like tn. 7- and 4-membered rings are still less stable than both 5- and 6- membered
rings. It seems that 5 membered ring has the least strain than others. One cannot equate the strain in a
polar molecule like diamines with cyclohexane ring strain having least strain.

CH2 CH2 CH2

CH2 CH2
H2N NH2 H2N NH2
>
n+ n+
M M

[Ni(H2O)6]2+ + 3 en [Ni(en)3]2+ + 6H2O KF = 2.0 × 1018

[Ni(H2O)6]2+ + 3 tn [Ni(tn)3]2+ + 6H2O KF = 1.86 × 1012
(tn = trimethylenediamine; H2N–CH2–CH2–CH2–NH2)
Cause of Chelate Effect:
The only factor which is responsible to make the numerical value of G large and hence makes
the KF value larger is the ENTROPY factor. H values(-ve) are more or less same in chelates and
equivalent non-chelates. But the increase in entropy in the chelate is large.
[Ni(H2O)6]2+ + 6NH3 [Ni(NH3)6]2+ + 6H2O (1)
[Ni(H2O)6]2+ + 3 en [Ni(en)3]2+ + 6H2O (2)
In equation (1), 7 particles have changed into 7 particles while in equation (2), 4 particles have changed
into 7 particles. Hence S is more +ve in second case which makes G more negative in the Gibbs
Helmholtz equation. So KF for chelates are much larger.
G = H – TS
So chelate effect is primarily entropy driven.
N.B: (1) More is the number of rings in chelate more is the stability of the complex(while keeping the
CN constant).
[Ni(dien)2]2+ (four rings) > [Ni(en)3]2+ (three rings)
EDTA, DTPA complexes are therefore very stable as it forms 5 and 7 rings respectively.
(2) Ring size also determines the stability of chelates. 5- and 6- membered rings are most stable.
The complexes of en, dien, trien, EDTA give 5-membered ring(s).
4- membered rings are very unstable due to angle strain. Therefore ligands like CO32– and SO42–
often behave like a monodentate ligands, not bidentate(flexidentate). 7-. 8- and 9- membered rings are
less stable than 5- and 6-membered rings. This is because the increase in entropy in these complexes
are relatively less.
SAQ: Arrange [Cr(en)3]3+, [CrCl6]3-, [CrF6]3-, [Cr(dien)2]3+ and [Cr(NH3)6]3+ in order of increasing stability.
Solution: First arrange in the order of increasing base strength for the donor atoms in ligands. More the base
strength more is the stability. Then further grade according to chelate effect if any when the donor atoms are
same. Chelates are more stable than non-chelates. Then further grade accoring to the number of chelate rings
produced.
[CrCl6]3- < [CrF6]3- < [Cr(NH3)6]3+ < [Cr(en)3]3+ < Cr(dien)2]3+

(7) Macrocyclic Effect:

Macrocyclic ligands or macrocycles are themselves cyclic and and polydentate. Examples like
porphine, cyclam and crown ethers are already given before. The stability of a complex with macrocyclic
ligands is more than the equivalent open chain chelating ligands and monodentate ligands. This is
called macrocylclic effect. For example, Cu2+ complex with cyclam(macrocyclic tetradentate amine
ligand) is much more stable than [Cu(en)2]2+ with equal donor atoms and CN. Similarly, the complexes
with crown ethers are more stable than those produced from oxalato ligands keeping CN fixed.
Hemoglobin and Chlrophyll are such complexes of Fe2+ and Mg2+ respectively with porphyrin
ligands which are very stable.
The important difference between macrocyclic ligands and open chain chelating ligands is that
in the former the cavity size is fixed for a particular ligand and it can accommodate only selective
metal ions more efficiently which fits with the size of the cavity and forms a much more stable complex.
For example the 18-crown-6 forms more stable complex with K+ ion than Na+ ion as the size of the
smaller Na+ ion does not fit well in the cavity of the crown ether.
The macrocyclic effect is both driven by entropy and enthalpy. There is a greater increase in
entropy and greater lowering of enthalpy in this case during complex formation. Hence the formation
constant is very large.

(8) Steric Effect:

Sterically hindered or crowded ligands form less stable complex than less or unhindered ligands.
For example N,N, N’, N’–tetramethylethylene diamine forms less stable complex than en.
(CH3)2N–CH2–CH2–N(CH3)2 complex < H2N–CH2–CH2–NH2 complex

(9) Surrounding Conditions:

Surrounding conditions like heat, light or pH also affects the stability of complex. A complex
may be unstable in presence of light or heat. Some complexes are unstable at lower pH and some at
higher pH. This is due to reactions occuring at different surrounding conditions.
Metal Carbonyls :
Carbonyl(CO) is a -doner and -accetor ligand. It is a neutral ligand too. Transition metals form metal
carbonyls in their zero OS. This fact, distinguishes the metal carbonyls from others in terms of formation
and the bonding behaviour. In most of these complexes, 18-e electron rule is meticulously adhered to.

Types: (a) Mononuclear :

Formula : [M(CO)n]
: where 2n = difference in the number of electrons between metal atom and the nearest noble gas.
Examples: [Ni(CO)4], [Fe(CO)5], [Cr(CO)6]
Exception: [V(CO)6] (it violates 18-e rule)
(b) Dinuclear(Binuclaer) :
Formula : [M2(CO)2n-1]
Examples: [Co2(CO)8], [Fe2(CO)9], [Mn2(CO)10]
(c) Trinuclear:
Formula: [M3(CO)3n–3]
Examples: [Fe3(CO)12]
(d) Tetranuclear:
Formula: [M4(CO)4n–6]
Example: [Co4(CO)12]
Geometry : [Ni(CO)4] : Tetrahedral ; [Fe(CO)5]: Trigonal bipyramidal [Cr(CO)6] : Octahedral
All these three complexes are diamagnetic.

Bonding in Metal Carbonyls:

To explain the bonding in metal carbonyl, a simple mononuclear complex like [Ni(CO)4] can be taken.
Let us discuss the bonding of the metal with ony one CO in the light of VBT. We shall mix up MOT
whereever we feel convenient particularly for CO. This is not according MOT(LFT) theory of complexes.
This is basically VBT. The lone pair on carbon present in a sp-hybrid oribital(VBT) or 2s* orbital(MOT)
directly overlaps with one sp3 hybrid orbital of Ni atom to form a -bond. Here CO acts as donor.
Again a filled d-orbital of metal(say 3dyz) forms a
-bond(d-p backbonding) with the vacant anti-
bonding orbital of CO(2py* MO). Thus there is
double bond character between M–C bond(though
not a M=C) as there are more than one CO ligands
all of which cannot form double bonds at a time.
So the resonance contribution makes the bond
order(BO) of M–C bond greater than 1 (less than
2). Due to backbonding the there is polarisation of
the -bonds in CO and thus the bond order in CO
becomes less than 3. This is reflected in the bond lengths of M–C and C–O bonds. M–C bond length in
metal carbonyls is lower than M–C bond in metal alkyls, where there is no backbonding. Similarly the
bond length of C–O bond in the complex is greater than that in CO.

N.B: This type of bonding occurs in all ligands which have multiple bonds like CN–, NO, NO+, CH2=CH2
etc. which are called -donor and-acceptor ligands.
Structure of Polynuclear Carbonyls:

[Co2(CO)8]: In the second structure, we find there are three terminal CO ligands on each CO. There is
a Co–Co bond. Also there are two two CO briding ligands between the two metal atoms. It has another
isomer in which there is no briding CO ligands. In stead, each metal atom is bonded to 4 terminal CO
ligands. Rh and Ir forms similar type(latter type isomer) complexes.
[Mn2(CO)10] : In the first structure, we find that there are five terminal CO ligands bonded to each Mn
atom. There is no bridging CO ligands in this case.
[Fe2(CO)9] : There are three terminal CO on each Fe and two bridging CO and one Fe–Fe bond. In Ru
and Os complexes of similar type, there is one briding CO and four terminal CO on each metal atom.

O
CO
C CO
OC Co
O
O
C CO CO
OC C
OC Co
OC Fe Fe CO Co CO
CO OC
OC
Co C O
Fe C CO
OC CO OC
OC CO O

[Fe3(CO)12] : There are two bridging CO between two Fe atoms, which have three terminal CO each.
The third Fe has four terminal CO. In Ru and Os complexes of similar type, there is no bridging CO and
each Fe is bonded to four terminal CO.
[Co4(CO)12]: There are three bridging COs between the three Co atoms each of which is bonded to two
terminal COs. The fourth Co is bonded to three terminal COs. The Co atoms are sitting on the corners
of a tetrahedron and each Co is bonded to the other three Co atoms by Co–Co bonds. In Rh and Ir
complexes of similar typ, there is no bridging CO and each Co is bonded to three terminal COs.

Metallocenes(Sandwich Compounds):
When organic species having more than one carbon atoms particularly cyclic ligands complex with a
metal ion, often the metal ion is sandwiched between the organic ligands on either side of it. Such
compounds are called metallocenes. Ferrocene is a classic example of metallocene. In ferrocene, the
Fe2+ is sandwiched between two cyclopendadienide ion.
Hapticity and Haptic Bonds: Organic group(ligand) can be bound to a single metal ion via one, two, three, four
or more carbon atoms simultaneously. This is unlike of the ligands which we have so fare studied in which one
or more donor atoms are bonded to a single metal ion independent of each other. For example in ethylene
diamine, the two amino N atoms bond to the metal ion independently and the intervening CH2 groups do not
bond with the metal ion. Such ligands are expressed in terms of their denticity i.e mondentate, bidentate,
tridentate and so on. But in organic structures in which all the carbon atoms lying under a composite delocalised
pi- electron system can simultaneously bond with the metal ion. Such ligands are expressed in terms of their
hapticity. Hapticity is the number of carbon atoms with which the ligand is bonded to the metal ion. Such bond
are called haptic bonds. In the ferrocene structure shown, all the five carbon atoms of each cyclopentadienide
ion is bonded to the Fe2+ ion. So cyclopentadienide ion is a pentahapto ligand as its hapticity is 5. All the bonds
shown in broken lines are haptic bonds.
The symbol  is given for haptic ligands with its hapticity given as superscript.
Monohapto: 1 : CH3– or R– bonded through one carbon atom
Dihapto : 2 : CH2=CH2, bonded through two carbon atoms.
Trihapto : 3 : CH2=CH–CH2– carbanion.
Pentahapto: 5 : Cyclopentadienide ion.

Examples:
(1) Ziese’s Salt : K[PtCl3(2-C2H4)].H2O. Complex Ion: [PtCl3(2-C2H4)]–
It is a square planar complex. There is one ethylene ligand whose
hapticity is 2. The alkene C=C is approximately perpendicular to
PtCl3 plane.
The bonding involves overlpap of filled -orbital of the ethylene
with a vacant d-orbital of the metal to form a -bond, together with
-backbonding from an occupied d-orbital of the metal with the
vacant *-antibonding orbital of the ethylene. As a result, the C–C
bond order in ethylene is decreased, leading to increase in C-C
bond length. This interaction changes the hybridisation of carbon
atoms changing from sp2 towards sp3, which bends the hydrogen
atoms on the ethylene away from the metal. So there is one  and one 
bond between metal and ligand.
N.B: Ziese’s salt is not a Sandwich compound though it contains haptic
bonds with ethylene.

(2) Ferrocene : [Fe(5-C5H5)2] : Iron(II) biscyclopentadienide

IUPAC name: bis(5-cyclopentadienyl)iron(II)
• Ferrocene is a very stable organo metallic compound containing
Fe ion sandwiched between two aromatic cyclopentadienide ion [C5H5)–
2+
] ,
which is a pentahapto ligand. Since 18-electron(six  - e from
each ligand and six d - electrons from Fe2+) is satisfied in the
complex, it is very stable. MOT explains the bonding in it very
clearly which we shall discuss here. There are multiple -bonds
both forward and backward as well as  - backbonding in this
compound. MOT(LFT) gives a clear idea on its bonding, which
we will not discuss here. The C–C bond length is 1.4Å and
C–Metal bond length is 2.04Å. Upto 164K, the two
cyclopentadienide rings are staggered and below that they are
eclipsed.
Ligand Field Theory(LFT) :
VBT and CFT could not explain all the properites of the TM complexes independently They had their limiations.
Ligand Field Theory(LFT) was an advancement over Crystal Field Theory which makes use of MOT and
explains all types of bonding interactions(both sigma and pi) between ligands and metal ion without sacrificing
the advantage of CFT. While VBT talked about only sigma bonding interactions and shapes of complexes,
CFT was silent on covalent bonding aspect, as the presumption was the bond was electrostatic(ionic). MOT
has been used in LFT in such a manner that the d-electrons present in the t2g and eg sets(for Oh complex) as
per CFT are also similarly present in the corresponding MOs in LFT. So not only the colour and magnetic
properties of complexes can be explained like CFT, the cause of relative strengths of ligands in spectrochemical
series can be explained. We shall be dealing with this theory here in the most simplistic manner just to introduce
the beginners about it as the higher secondary syllabus does not remmend it.
LFT in Oh complexes:
In this case, the 6 atomic orbitals of the metal ion namely (n-1)d(eg set), ns and np will combine with 6
nonbonding electron orbitals(called sigma orbitals) of the six ligands to give six bonding MOs and six antibonding
MOs. The t2g set of orbitals remain as three non-bonding MOs in the same level. All the electrons from the
metal ion and the ligands will be redistributed in the MOs. After that we shall find that 12 electrons(presumed
to be those contributed by the ligands) occupy the six bonding MOs and the remaining 5 MOs(t2g and eg*) will

No pi-bonding
interation

contain the rest of electrons(presumed as belong to metal ion). Finally we can play with these 5 orbitals exactly
like t2g and eg in the CFT with the same number of d-electrons as was present in free metal ion. The difference
is that in LFT, it is eg* (not eg) which is an antibonding MO. Further t2g level can go down depending on the
presence of pi-bonding interactions, that we shall see shortly.

Example : [CoL6]3– : (L– is a monodentate ligand) : d6 configuration

Metal Orbitals undergoing combination :
3d: t2g and eg (the five orbitals are degenerate); 4s : a1g(one orbital)
4p : t1u (triply degenerate) (4s and 4p are often vacant)

Energy order : (eg + t2g) < a1g < t1u

Ligands Orbitals undergoing combination: These are six degenerate MOs formed by the combination
of the nonbonding(-orbitals) orbitals of the six ligands and have the same designations as the orbitals
of metal ion i.e a1g(same symmetry as 4s of metal ion), t1u(3 MOs having same symmetry as 3p orbitals
respectively) and eg( two MOs having same symmetry as the two d-orbitals having lobes along axes).
Note that a1g, t1u and eg sets of six degenrate MOs from ligands have lower energy than (eg+t2g) set of
metal ion.

N.B: The t2g set of orbitals in the metal ion have no matching symmetry counterpart in the ligands, as their lobes
are lying in between the axes. Hence these three AOs remain as nonbonding MOs at the same level.

In the above diagram, we can see that the there are six bonding MOs having same designations as a1g, t1u
and eg having lower energy than all the combining AOs/MOs in the energy order
a1g < t1u < eg
and six antibonding MOs, two of which(a1g* and t1u*) have greater energy than the all the combining
AOs/MOs and one of them eg* has energy level above t2g(nonbonding) MOs. Hence there is gap(o)
between t2g(nonbonding MO) and eg* MO which is called o for octahedral complex. So the CFT
concept can be extended to these two sets to explain many properties.

In the example given above, six electrons from Co3+ and 12 electrons from six ligands, a total of 18
electrons are to be distributed in the MOs. Out of this 12 occupy in the six bonding MOs. The remaining six
now are left to be filled in t2g and eg set according to the value of o compared to Pairing energy.
Sigma() bonding: The six lower energy MOs(a1g, t1u and eg) are responsible for -bonding, to form
six bonds.

Strength of ligand(o) :
There are three categories of ligands on the basis of their ovalues, which, in turn, due to the nature of their
bonding type.
(a) Strong/High Field Ligands having large o values : These are -donor and -
acceptor ligands (eg CO, CN–, NO2–, PPh3 etc)
(b) Weak/Low Field Ligands having low ovalues : These are -donor and also -
- -
donor ligands (eg I , Br etc.)
(c) Intermediate Field Ligands having intermediate o values: These only -donor
lignads (neither -donors or -accetors) eg. H2O, NH3
It is the pi bonding in complexes which not only strengthens the bonding but also weakens the bonding. The
order in spectrochemical series is understood from LFT.
pi() bonding : According to LFT, the the filled or vacant p(or )-orbitals(AOs or MOs) of ligands combine
with the non-bonding t2g orbitals of metal ion to form metal-ligand -bonding. There are three catetories.

(a) pi-acceptor ligands: The ligands

having multiple bonds like CO, CN–, NO2–
etc have their vacant LUMO(*) orbital to
accept electron pair from metal. The
combination of these high energy LUMOs
with t2g orbitals of metal ion makes the (t2g)
bonding MO and antibonding MO(*) and
the latter lies above eg*. Thus gap between
(t2g) and eg* which is nothing but the o
becomes large. This is called Metal – ligand
backbonding. Such ligands have large values
o and are called Strong field ligands.
(In the diagram; ‘A’ represents no pi-
bonding while C represents the -bonding
for pi-acceptor ligands, discussed above and B represents the p-donor ligands to be discussed below.)
(b) pi-donor ligands: The anionic ligands which have three filled p- non-bonding orbitals like I–, Br,
S2– etc can combine with t2g orbitals to give -bonding MOs containing the ligand electrons(as if) and *(t2g)
antibonding MO containing the metal ion’s d-electrons(as if). In this case *(t2g) remains below eg* level. So
that the gap beweeen *(t2g) and eg* which is nothing but o is small. These are called Weak field Ligands.
 (c) Neither -donor nor -acceptor Ligands: Neutral ligands like H2O, NH3 cannot donate electrons
to metal ions for pi-bonding. Once one pair is donated for -bonding, the O/N atom carries positive formal
charge which does not allow the other two or one filled p-orbital respectively to combine with three t2g orbitals
of metal ion. The other main reason is that the combination lacks symmetry as O and N have less than 3 filled
p-orbitals for combination. Such ligands have intermediate o values as there is no pi-bonding contribution to
offset the o values. So these are intermediate field ligands. These lie in the border line between strong and
weak field ligands. NH3 being stronger than H2O due to greater basicity of the former.
Example: Draw the LFT diagram for the complex [Cr(CO)6]:
3d5, 4s1 (Cr0) : 6e
In the digram shown(borrowed from Google source) (t2g) is written as t2g and * is written as t2g*. Since CO
is a pi-acceptor ligand, o value is larger than Pairing energy(P). Hence all the 6 electrons have been arranged
in the (t2g) orbitals. Hence it is diamagnetic.

Advantage of LFT

The real cause of the spltting power of ligands i.e the order in the spectrochemical series could be
known. The nature of covalent bonding intereactions(both sigma and pi) could be studied in details in this
theory. Also all other properties like colour, magnetic etc can also be well explained by this theory.

Disadvantage:
The shape of the complex cannot be explained by MOT like CFT.
Jahn-Teller Effect(JTE)/Jahn Tellar Distortion(JTD):
JT Theorem(General): Any non-linear molecular system in a degenerate electronic state will be unstable
and will undergo distortion to form a system of lower symmetry and lower energy, thereby removing the
degeneracy.
In a non-linear complex molecule, if the degenerate orbitals(t2g and eg) are asymmetrically occupied, it is
unstable. A distortion will occur which removes the degeneracy and stabilizes the system by lowering of the
energy due to lowering of symmetry. This is called Jahn-Teller Distortion(JTD) or Jahn Teller Effect(JTE).
Breaking down of symmetry is the cause of stability in this case.
(This is opposite to the increase in stability i.e decrease in energy when symmetry is increased. In this case a
higher Oh point group symmetry is converted to a lower distorted octahedral symmetry, which falls into D4h
point group. Many non-linear systems show this JTD, in which their stability increases by lowering down the
symmetry. Eclipsed conformation of ethane is more symmetrical than staggered conformation, although latter is
more stable.)

* JTE is more prominent in Oh complexes as repulsion between ligands and occupied d-orbitals is more.
* d1, d2, high and low spin d4, low spin d5, high spin d6, low and high spin d7 and d9 metal ions are
asymmetrically filled and show JTE.
* d3, high spin d5, low spin d6, d8 and d10 metal ion have symmetrically filled d-orbitals and do not show
JTE.
* High spin d4, low spin d7 and d9 metal complexes show pronounced JTE, as the asymmetry is present
in the eg set, whose lobes are directed towards axes(hence towards ligands). Other show small JTE as asymmetry
is present in the t2g set whose lobes lie in between the axes(not directed towards ligands). d9 metal complexes
show maximum JTE.
HS d4 : Cr2+, Mn3+ LS d7 : Co2+, Ni3+ d9 : Cu2+, Ag2+
* Tetrahendral complexes show little JTE as the lobes of d-orbitals are not directed towards the ligands.

* Types of Jahn Teller Distortions in Oh complexes

(a) Z-out distrotion(Z-elongation): The two trans ligands along z-axis are stretched
out. In other words, an elongation of the axial bonds occurs,
thereby the z-factored orbitals acquire lower energy in each set.
z-out distortion is the common occurrence when asymmetry is
present in eg set.
(b) Z- in distortion(Z-compression):
The two trans ligands along z-axis are compressed. In other
words, there is shortening of the axial bonds, thereby the z-
factored orbitals acquire higher energy in each set. Usually d1-
complex show z-in distortion. Example: [Ti(H2O)6]3+.

Z-out Distortion: It is most significant in Cu2+ Oh complex. These are really distorted Oh with axial ligands are
stetched out with longer bond lengths than the sqaure planar bonds. Due to strong JTE, the Oh splitting
increases and so also CFSE. This stabilises the complexes. Cu2+ Oh complexes have highest stability due
to JTE(Refer Irving Willam order).
In [CuF6]4–, Four Cu-F bond lengths are shorter i.e 193 pm while the
two distorted axial Cu-F bonds are longer i.e 227 pm. Similar is the
case with [Cu(H2O)6]2+.
Imp: Cu2+ cannot form [Cu(en)3]2+, as the axial bonds cannot
accommodate the bidentate ligands. Only [Cu(en)2(H2O)2] is formed
in only trans form. Cis form is unstable.
JTE is also noticed in [Cr(H2O)6]2+ which is HS d4 complex and in
[Co(NH3)6]2+ which is LS d7 complex.
Due to splitting of eg set in distorted Oh gemoetry, the UV/Visible
absorption peak also splits into doublet.
Application of Complexes:
l. Dyes and Pigments: Coordination compounds have been used from the earliest times as dyes and
pigments, for example madder dye which is red, was used by the ancient Greeks and others. It is a complex of
Hydroxyanthraquinone. A more modern example is the pigment copper phthalocyanine, which is blue.

2. Analytical Chemistry: You have already encountered many such uses during the laboratory course.

(a) Colour Tests: Since many complexes are highly coloured they can be used as colourimetric reagents
e.g. formation of red 2,2'-bipyridyl and l,l0-phenanthroline complexes as a test for Fe(II)

(b) Gravimetric Analysis: Here chelating ligands are often used to form insoluble complexes e.g.
[Ni(dmg)2] and [Al(oxine)3] (see laboratory manual).

(c) Complexometric Titrations and Masking Agents: An example of this is the use of EDTA in the
volumetric determination of a wide variety of metal ions in solution, e.g. Zn2+, Pb2+, Ca2+,Co2+, Ni2+, Cu2+, etc.
By careful adjustment of the pH and using suitable indicators, mixtures of metals can be analysed, e.g. Bi3+ in
the presence of Pb2+ (see laboratory manual). Alternatively, EDTA may be used as a masking agent to remove
a metal ion which would interfere with the analysis of a second metal ion present.
(d) Salt Analysis: While detecting Cd2+ in presence of Cu2+, cyanide complexes i.e [Cd(CN)4]2– and
[Cu(CN)4]3– are prepared. The former is very unstable while the latter is very stable. On passing H2S gas
yellow Cds is precipitated without affecting the copper complex.

3. Sequestering Agents: Related to their use as masking agents is the use of ligands for "sequestering"
i.e. for the effective removal of objectionable ions from solution in industrial processing, e.g. EDTA is used to
"soften" water. The addition of EDTA to water is used in boilers etc., to prevent "scaling" or build up of
insoluble calcium salts.

4. Extraction of Metals: Sometimes certain metals can be leached from their ores by formation of
stable complexes e.g. Ag and Au as complexes of cyanide ion forming [Ag(CN)2]+ and [Au(CN)2]– respectively
in the Mc Arthur’s process.

5. Bio-Inorganic Chemistry: Naturally occurring complexes include haemoglobin, chlorophyll, vitamin

B12 etc. EDTA and other complexing agents have been used to speed the elimination of harmful radioactive
and other toxic elements from the body. (e.g. Pb2+). In these cases soluble metal chelate complexes are
formed.
6. Chemo-therapy: an example here is the use of cis-[PtCl2(NH3)2]as an anti-tumour drug.
7. Pb and other Heavy Metal Poisoning: Pb, Hg, As, Co, Ni etc are removed easily with EDTA
ligand by administering intravenous injection of CaNa2(EDTA) which is soluble in blood. Pb2+ forms a
complex easily with EDTA and separated from blood in the urine.
Sturctures of Hydrated Crystals:
Many hydrated crystals of TM ions exist as complexes. Mostly 4 or 6 H2O molecules lie
inside the CS and one or more H2O, if any, lie outside the CS. Two examples are given to
explain this in some details.

CuSO5.5H2O (Blue Vitriol)

It has a typical crystal structure. Cu2+ has a

coordination number of 6 with a distorted octahedral
geometry. Cu2+ is covalentlty(coordinate) bonded to
4 H2O molecules lying in one plane with shorter bond
length. [Cu(H2O)4]2+ units are interconnected by
sulphate ions to form polymeric chain. Each Cu2+ is
covalently(coordiante) bonded to two sulphate(SO42–
) which occupy the distorted axial positions, one above
and one below the [Cu(H2O)4]2+ plane. Since each
sulphate ion is bonded to two Cu2+ ions, only one
SO42– is counted for the empirical formula of
CuSO5.5H2O. The fifth H2O molecule is connected
to two parallel sulphate ligands by hydrogen bonds.
This molecule is also hydrogen bonded with H2O
molecules in the coordination sphere(not shown in the
diagram). Since two such H2O molecules are H-
bonded to two parallel units, one of them is counted for the empirical formula.
So we can write the formula of blue vitriol as [Cu(SO4)(H2O)4].H2O. The Cu–OSO3– bond is greater than the
Cu–OH2 bond as the sulphate ions occupy the Z-out distorted positions. This is because Cu2+ shows pronounced
Z-out Jahn Teller Distortion effect in Oh geometry.
Hence in the crystal there is (a) ionic bond (the axial bonds have significant ionic character), Coordinate bonds,
covalent bonds(within H2O and SO42–) and hydrogen bonds.
When blue vitriol is dissolved in water, it forms [Cu(H2O)6]2+ and SO42– ions. The former ion is distorted
octahedral with two longer axial bonds and four shorter equatorial(planar) bonds.

FeSO4.7H2O(Green Vitriol)

It is [Fe(H2O)6].SO4.H2O. Fe2+ is coordinated with six H2O with octahedral geometry, and the seventh H2O
molecule is connected to SO42– and H2O molecules in Coordination sphere by hydrogen bonding. The crystal
dissolves in water forming [Fe(H2O)6]2+ and SO42– ions.