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01 Coordination Complex Compounds Plus2 2nd Year
01 Coordination Complex Compounds Plus2 2nd Year
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.
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
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).
(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)
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
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
CH2 CH2
CH2
NH CH2
Examples: Diethylene triamine(dien) : H2N (neutral)
NH2
N
Terpyridine(Terpy) : (neutral)
N N
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
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
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)
–
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.
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)
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]
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
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)
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)]
a b a c a b
M M M
d c d b c d
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)
b b
a b a a
M M
a a a a
a b
cis trans
Ex: [CoCl2(NH3)4]+ :
b
b
a c a a
M M
a a a a
a c
cis trans
Ex: [CoCl(NO2)(NH3)4]+
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.
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)
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]
a A a A
M M
a A a
A
A A
cis trans
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)]+
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.
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)
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]–
cis-cis-cis
a a
a b b a
M M
c b b c
c c
d/l pair
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
A A
A a a A
M M
A a a A
A A
d/l pair
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
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
7. [M(AA)3] type:
A A
A A A A
M M
A A A A
A A
d/l pair
8. [M(AA)2BB] type:
This also exists as d/l pair like the previous case.
Ex: [Co(ox)(en)2]+
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)
No. of GIs
(Diastereoisomers) 2 2 2 3 4
No. of enantiomeric – – – – 1
pair
_______________________________________________________
Total no. of
Stereoisomers 2 2 2 3 5
No. of GIs
(Diastereoisomers) 5 6 9 15
No. of enantiomeric 1 2 6 15
pair
_______________________________________________________
Total no. of
Stereoisomers 6 8 15 30
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
No. of GIs
(Diastereoisomers) 5 6 10
No. of enantiomeric 5 5 10
pair
_______________________________________________________
Total no. of
Stereoisomers 10 11 20
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
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:
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.
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.
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.
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.
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.
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
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
[Ni(CN)4]2– : 3d 4s 4p
dsp2 hybridisation
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–
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 '
Ek
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.
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:
LS :
eg
0
HS:
eg
0
( No. of Unpaired electrons = 4)
t2g
d5 metal ion: (eg Mn2+, Fe3+):
LS:
eg
0
HS:
eg
0
( No. of Unpaired electrons = 5)
t2g
0
HS:
eg
0
( No. of Unpaired electrons = 4)
t2g
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):
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.
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).
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.
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
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
t2g
3 3+
d : Cr complexes
eg
t2g
d8 : Ni2+ complexes
eg
t2g
d9 : Cu2+ complexes
eg
t2g
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.
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
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 1034 Js 3 108 ms 1
t 9
3.65 1019 J
545 10 m
9
0 t 8.3 1018 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.
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
0.0860
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.
d x2- y2
dxy
barycentre
dz 2
dyz ,dzx
SP splitting
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
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
eg
0
t2g
12 3 9
CFSE = 5 0 5 0 3P 2 P 5 0 P = –37000 cm–1.
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
h
e
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 1019 J
535 109 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 1034 3 108
0 3.75 1019
9
530 10 m 530nm
It absorbs green light and appears red.
_________________________________________________________________________________
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
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.
M+ L k1
[ML1]
k2 [ML2]
[ML1] + L
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
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.
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
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.
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.
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.
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.
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.
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.