Coordination Compound - Theory, Solved Ex. Module-3-2
Coordination Compound - Theory, Solved Ex. Module-3-2
Coordination Compound - Theory, Solved Ex. Module-3-2
Triethylene tetramine
(Trien)
(E) Pentadentate ligands : They have five donor
atoms. For example, ethylenediamine triac- (g) Generally the chelate complexes with 5
etate ion. or 6 membered rings are more stable.
(h) Out of these, 5 membered rings are very
stable when they involve saturated ligands.
(i) On the other hand 6-membered ring
structures acquire maximum stability when
they involve unsaturated ligands contain-
ing conjugate double bond. This is due
to the resonance effects involving metal
d-orbitals and ligand p-orbital electrons.
3.2.2 Classification of ligands on the basis of
Ethylenediamine triacetato ion donor and acceptor properties of the ligands
(A) Ligands having one (or more) lone pair
(F) Hexadentate ligands : They have six donor atoms.
(or pairs) of electrons
The most important example is ethylenediamine
(a) Ligands which contain vacant -type orbitals
tetraacetate ion.
that can receive back donated e¯ from
M-ion in low oxidation state.
e.g.: CO, NO, CN, NC, R–N=C, R3P, R3As
–dipyridyl, o-phenanthroline
(b) All these ligands also have filled donor
orbital in addition to vacant -type ac-
ceptor orbitals.
(c) Thus in there complexes both metal and
ligand function as donors and acceptors
Ethylenediamine tetraacetato ion (EDTA) 4–
(M
L)
(G) Chelating ligands. (d) Ligands which do not have vacant orbitals
(a) Polydentate ligands whose structures permit to receive back donated electron from metals
the attachment of two or more donor sites eq. H2O, NH3 F.
(B) Ligands having no lone pairs of electrons 3.5 Oxidation state
but have p bonding electron eq. Ethyl- (a) It is a number which represents the
ene, benzene, cyclopentadenyl-ion electric charge on the central metal atom
Note: (1) Polydentate ligands have Flexidentate of a complex ion
character it is not necessary that all the (b) For example, the O.N. of Fe, Co and
donor atoms present in the polydentate Ni in [Fe(CN) 6] 4– , [Co(NH 3) 6 ] 3+ and
ligands should form coordinate bonds with Ni(CO)4 is +2, +3 and zero respectively
central metal atom or ion. (c) The charge of the complex is the sum
(2) There are certain ligands which have two of the charges of the constituent parts.
or more donor atoms but during formation
of complexes only one donor atom is 3.6 Effective atomic number (EAN)
attached to metal ion. Such ligands are (a) In order to explain the stability of the
called ambidentate ligands such as CN, complex, Sidgwick proposed effective
CNS atomic number
(b) It can be defined as the resultant
3.3 Coordination number : number of electrons with the metal atom
(a) The number of atoms of the ligands that or ion after gaining electrons from the
are directly bond to the central metal donor atoms of the ligands.
atom or ion by coordinate bonds is known (c) The EAN generally coincides with the
as the coordination number of the metal atomic number of next noble gas in some
atom or ion. case.
(b) It is actually the number of coordinate (d) EAN is calculated by the following
covalent which the ligands form with the relation EAN = atomic number of the
central metal atom or ion metal–number of electrons lost in ion
(c) Some common coordination numbers formation + number of electrons gained
exhibited by metal ions are 2,4,6. The from the donor atoms of the ligands
light transition metals exhibit 4 and 6 (e) The EAN values of different metal in their
coordination numbers while heavy tran- respective complexes are tabulated as
sition metals may exhibit coordination follows
number more than 6
(d) For example, the coordination number of various terms used in coordination
Examples
Ni in the complex [Ni(NH3)4]Cl2 is 4 and based on compounds
that of Pt in the complex K2[PtCl6] is 6
3.4 Coordination sphere : Ex.3 The EAN of nickel in Ni(CO) 4 is
(A) 36 (B) 38
(a) The central metal atom and the ligands (C) 28 (D) 54
directly attached to it are collectively termed
as the coordination sphere Sol. (A) Effective atomic no. (EAN)
(b) Coordination sphere is written inside square = at. no. of central atom – oxidation state
bracket, for example [Co(NH3)6]3+ +2 x (no. of ligands)
(c) The central metal atom and the ligands = 28 - 0 + 2 x 4 = 36
inside the square bracket behave as a Ex.4 The charge on cobalt in [Co(CN) 6]3– is
single entity
(A) –6 (B) +3
(d) The part outside the bracket is called
ionisation sphere. (C) –3 (D) +6
(e) The species present in the coordination Sol. (B) The algebraic sum of oxidation no. of
sphere are nonionizable all atoms in a complex ion is equal to charge
(f) The species present in the ionization sphere on that ion,
are ionisable i.e., a + 6 x (–1) = –3, a = + 3
Ex.5 Co-ordination number of Co in [Co (NH3)6]2+
is
(A) 4 (B) 5
(C) 6 (D) 8
Sol. (C) Co-ordination number is equal to total
number of ligands in a complex.
Complex Matal At. No. Coordination Effective
(Oxid. state) of matal number atomic number
Number of 0 1 2 3 4 5
unpaired
electrons
Draw back of V.B. Theory Ex.15 Find out the hybridization, geometry and mag-
(i) It describes bonding in coordination com- netic moment of the complexes :
pounds only qualitatively (i) [Co(NH3)6]3+
(ii) It does not offer any explanation for the
(ii) [Cr(CN)6]3–
optical absorption spectia of complex
Sol. (i) The oxidation state of cobalt in the com-
(iii) It does not describe the detailed magnetic
plex [Co(NH3)6]3+ is +3
properties of coordination compounds. The electronic configuration of Co3+ ion is :
5.4 Crystal field Theory
3d 4s 4p
This is the more advanced theory and satis-
factorily explains the optical absorption spec-
tra and magnetic properties of complexes
which were not explained by V.B.T. But its [Co(NH3)6]3+
details are beyond the scope of this text. Rearrangement
Examples
Octahedral, zero magnetic moment
based on Bonding in coordination compounds
(ii) The oxidation state of chromium in the com-
7 plex is +3. The electronic configuration of Cr3+
Ex.12 When the configuration is d in a transition
metal, the paramagnetic susceptibility will be ion is
equal to 3d 4s 4p
(A) 3.87 B.M. (B) 2.68 B.M.
(C) 5.92 B.M. (D) 6.92 B.M.
Sol. The magnetic moment values in Bohr magne-
ton for 1 lone electron is 1.73, for 2 is 2.83, for [Cr(CN6)] 3+
3 is 3.87, for 4 is 4.90, for 5 is 5.92, for 6 is
Rearrangement
6.92 and so on. d7 configuration has three d 2sp 3 hybridizat ion
lone electrons, hence, = 3.87 BM.
= (a) Cr24
(a) Ni 28
(b) Co3+ ion 3d 4s 4p
(a) e¯ configuration of Ni
(b) e¯ configuration of Zn2+ 3d 4s 4p
3d 4s 4p
(b) e¯ configuration of Ni 2+
(c) Zn2+ in sp3 hybridised state 3d 4s 4p
dsp2
sp3 hybridised (d) The rearrangement is due to presence
of strong ligand CN¯. The four orbitals
(d) Zn (NH3)4]2+
make dsp2 hybridisation
(e) The shape of resulting complex is square
planar
NH3 NH3 NH3 NH3 (d) due to paired electrons it is diamagnetic.
Co-ordination numbers, Hybridised orbitals and geometry of some co-ordination compounds
Coordination Hybridised orbital Geometrical shape of Examples of
Number the complex complex
2 sp [Ag(NH3)2]+
Linear [Ag(CN)2]¯
3 sp2 [Hg3]¯
dsp2
The d-orbital involved is [Ni(CN)4]–2
4. dx2–y2 orbital [Pt(NH3)4]+2
of the inner shell, i.e. it
is (n – 1)dx2–y2 orbital
dsp3 [CuCl5]–3
5. The d-orbital is [MoCl5]0
(n - 1)dz2 orbital [Fe(CO)5]0
sp3d
5. The d-orbital is ndx2–y2 [SbF 5] –2 IF 5
orbital
Square pyramidal
d2sp3
When d-orbitals are (n-1)
d-orbitals (Inner orbital [Cr(NH3)6+3]
6. complexes) or sp3d2 [Ti(H2O)6]+3
When d-orbitals are [Fe(CN)6]–2
nd orbital (Outer orbital [Co(NH3)6]+3
complexes) In both cases [PtCl6]–2[CoF6]–3
p-orbitals are dz2 and dx2-y 2
orbitals.
Octahedral
L = Ligands indicated by white circles (same In the formation of [Ni(CN)4]2–, Ni2+ ion undergoes
or different) M = Central metal indicated by dsp2 hybridization, hence it is square planar
black circles. in shape
Examples
based on Shape of Complexes
3d 4s 4p
dsp3 7. ISOMERISM IN COMPLEXES
xx Electron pair donated by CO. (a) Compounds which have the same molecular
Ex.19 How would you account for the following : formula, but differ in their properties due
Ni(CO)4 possesses tetrahedral geometry while to the difference in structure ar called as
[Ni(CN4]2– is square planar. Isomers.
Sol. In the formation of Ni(CO)4, nickel undergoes (b) Isomerism is commonly considered, to be
sp3 hybridization, hence it is tetrahedral in
the characteristic of only organic compounds,
shape.
it is also found although less frequency among
3d 4s 4p
inorganic substances.
Ni(0)3d8 (c) Classification of isomerism :
Ni(CO)4
Rearrangement
sp 3 hybridizat ion
Type of isomerism
M M
b b b a
Cis Trans
(iii) [Pt (NH3)2Cl 2]
Pt Pt
Cl Cl H3N Cl
Cis(Cis-platin) anti cancer Trans
(iv) [Pt(NH3)2ClBr]
Cl NH3 Br NH3
Pt Pt
Br NH3 H3N Cl
Cis Trans
(v) Complexes with general formula, Mabcd can have three isomers.
a b a d a c
M M M
d c c b b d
(i) (ii) (iii)
–
CH2 NH2 NH2 CH2 CH2 NH2 O CO
Pt Pt
– – –
CO O O CO CO O NH2 CH2
(cis) (Trans)
9.3 Geometrical isomers with coordination number = 6
(i) [Fe(NH3)4Cl 2]
Cl NH3
H3N NH3 H3N Cl
Fe Fe
Cl py py Cl
Pt Pt
Cl NH3 H3N Cl
NH3 NH3
Pt Pt
Cl NH3 H3N Cl
I l
d-isomer Mirror -isomer
(iii) [M (AA) 3]n+ [Co(en)3]3+
3+ 3+
en
en en
Co Co
en
en en
2+ 2+
en
Cl en Cl
Co Co
H3N NH3
en en
gly
gly
gly
Cr gly Cr
gly
gly
(vi) [M (AA)B2C2][Fe(NH3)2(en)Cl 2]
Cl Cl
Cl Cl
en Fe Fe en
NH3 NH3
NH3 NH3
Mirror
Cis-d-isomer Cis--isomer
(vii) [M(AA)2B2][Fe(en)2Cl2]
en en
Cl Cl
Fe Fe
Cl Cl
en en
Mirror
Cis or trans-d-isomer Cis or trans--isomer
(i) Trans- [Fe(en) 2Cl 2] do not show optical (e) The forthcoming stability constant K’ is
activity due to superimposition of their [ ML 2 ]
mirror image. K1 = [ ML] [ L] its value is less than K
(ii) Some more examples are optically active:
[Cr(ox) 3] 3–;[Fe(dipy) 3] 2+; [Cr(ox) 2(H 2O) 2 ;
[Pt(en)3]4+ etc. (f) The higher the value of stability constant stabler
is the complex.
(g) The value of stability constants for some of
Examples Isomerism in Coordination the complexes are given below :
based on Compounds
Complex Stability constant
Ex.20 Which of the following sets is/are example(s) [Cu(NH3)4]2+ 4.5 x 1011
of co-ordination isomerism in complexes ?
(A) [Co(NH3)6] [Cr(CN)6] and [Co(CN6] [Ag(NH3)2]+ 1.6 x 107
[Cr(NH3]6] [Co(NH3)6]2+ 1.12 x 106
(B)[Cr(H2O)5Cl]Cl2.H2O and
[Co(NH3)6]3+ 5.0 x 1033
[Cr(H2O)4Cl 2]Cl.2H2O
(C) [Co(NH3)5Br]SO3 and [Cr(NH3)5 SO 4]Br [AgCl2]¯ 1.11 x 105
(D) [Pt(NH3)2Cl 2] and [Pt(NH3)4] [PtCl 4] [AgBr2]¯ 1.28 x 107
Sol. (A) When both positive and negative ions [Ag(CN)2]¯ 1.0 x 1022
are complex, co-ordination isomerism may
occur due to the interchange of ligands within [Cu(CN)4]2– 2.0 x 1027
the co-ordination sphere itself. e.g. [Co(NH3)6] [Fe(CN)6]3– 7.69 x 1043
[Cr(CN)6] and [Co(CN)6] [Cr(NH3)6] are two
co-ordination isomers, where ammonia and 10.1 Factors influencing the stability of com-
cyanide ligands have been changed within plex
the co-ordination sphere. 10.1.1 Nature of central ion -
Choices (b), (c) and (d) are examples of hydrate (a) The complex will be more stable for higher
isomers, ionisation isomers and polymerisation
isomers, respectively. Ch arg e
values of charge density
radius
Ex.21 Which of the following does/do not exhibit
(b) The higher the electronegativity of the central
optical isomerism ion, the greater is the stability of its
(A) tetrahedral complexes complexes
(B) square planar complexes (c) The higher the oxidation state of the metal
(C) octahedral complexes the more stable is the compound
(D) polynuclear complexes
Sol. A square planar complex does not exhibit 10.1.2 Nature of ligand
(a) A basic ligand is likely to easily donate
optical activity because it has a horizontal
its electrons. Thus a more basic ligand
plane of symmetry
will form more stable complex.
10. STABILITY OF COMPLEX (b) Chelating ligands form more stable
complexes as compared to monodentate
(a) A complex is formed in solution by the ligands.
stepwise addition of ligands to a metal
ion Stability and Characteristics of
Examples
(b) This can be expressed as follows M + L ML
where M = metal and L is ligand
based on Coordination Compounds
(c) The stability constant K for this reaction is
as shown Ex.22 [Cu(CN)4] 2– is more stable complex than
ML [Cu(NH3)4] 2+. Explain
K = [ M] [ L] Sol. The higher stability constant (K = 2 x 10 27)
(d) This metal can again get a ligand for Cu2+ + 4CN¯ [Cu(CN)4]2– than for
ML + L ML2 [Cu(NH3)4]2+ which is 4.5 x 1011 explains stability.
Ex.23 [Ti(H2O)6] 3+ is coloured while [Sc(H2O)6] 3+ is 11.2 –bonded organometallic compounds : This
colourless. explain type of compounds are generally formed by
transition metals. Some examples of –
Sol. Sc(H2O)63+ has no unpaired electron in its complexes are –
d subshell and thus d-d transition is not possible
whereas Ti(H2O)63+ has one unpaired electron Transition metals usually form the –bonded
complexes. Ferrocene, Dibenzene chromium,
in its d subshell which gives rise to d-d-
Zeise’s slat, etc. are some well known examples
transition, to impart colour. of the complexes belonging to this class.
+ NH3 py
Cl NH3
M
Pt
H3N HOH2N NO2
NH3
3+
Co =
Sol. CN– is strong field ligand and so it pairs up
the electrons leading to the formation of low 3d 4s 4p
spin complex which is diamagnetic. • • • • • •
[Co(NH3)6]3+ • • • • • •
[Fe(CN)6] 4– ;
2 3
Rearrangement d sp hybridization
2 3
d sp Octahedral, zero magnetic moment
6
3d 4s 4p
(ii) The oxidation state of chromium in the
•• •• •• •• •• ••
complex is +3. The electronic configuration
of Cr3+ ion is –
Octahedral, diamagnatic complex
F– is weak field ligand so it forms high spin 3d 4s 4p
3–
[Cr(CN)6] =
paramagnetic complex.
[FeF 6]4– :
• • • • • •
3 2 • • • • • •
sp d
2 3
Rearrangement d sp hybridizaton
•• •• •• •• •• ••
Octahedral, mag. moment
Octahedral, paramagnetic complex
= 3 (3 2) = 15 = 3.87 B.M.
Ex.8 [Fe(CN)6] 3– is weakly paramagnetic while
[Fe(CN)6]4– is diamagnetic, why ?
Sol. [Fe(CN)6]3– involves d2sp3 hybridization Ex.10 The magnetic moment of [MnCl4] 2– is 5.92
B.M. On the basic of its magnetic moment,
d s p
write configuration of Mn2+ in this complex.
Fe3+(d5)
Fe2+(d6)
unpaired electrons and so its possible
• • • • • • configuration may be Mn2+ in [MnCl4]2– =
[Fe(CN)6]4– • • • • • •
[Ar] 3d54s0
2 3
Rearrangement d sp hybridization
so hybridisation of Mn2+ in the given complex
All orbitals are doubly occupied, hence it is must be sp3.
diamagnetic in nature.
5
3d 4s 4p
Ex.9 Find out the hybridization, geometry and • • • •
[Fe(CN)6]4– • • • •
magnetic moment of the complexes :
3
(i) [Co(NH3)6]3+ (ii) [Cr(CN)6]3– sp hybridization
Ex.11 All the octahedral complexes of Ni2+ are outer Their electrical conductances in aq. solutions
orbital complexes, why ? are –
8 (A) 256, 0, 97, 404 (B) 404, 0, 97, 256
3d
(C) 256, 97, 0, 404 (D) 404, 97, 256, 0
Sol. Ni2+ :
Sol.(A) Coordination number of Pt is 6 hence
Thus only one 3d-orbital is available electrons
I K2[PtCl 6] – Three ions
pair up due to strong field ligand. Therefore ,
II [Pt(NH3)2Cl4] – Zero ions
d2sp3 hybridisation is not possible. Only
sp 3d 2 is possible which represent outer III [Pt(NH3)3Cl3]Cl – Two ions
complex. IV [Pt(NH3)5Cl]Cl3 – Four ions
Conductivity no. of ions
Ex.12 Ni(CO)4 possesses tetrahedral geometry while
[Ni(CN)4]|2– is square planar, why ? Ex.15 Determine the oxidation state of metal in
Sol. In the formation of Ni(CO)4, nickel undergoes the complex ion, [PtCl6] 2–.
sp3 hybridization, hence it is tetrahedral in Sol. Charge on the complex ion = Oxidation state
shape. of metal + charge on ligands
8
– 2 = x + 6 × (– 1)
3d 4s 4p
or x = + 4
Ni(0)3d8 :
The oxidation of Pt in the complex ion is +4.
Ni(CO)4 :
[Ni(CN)4]2– : • • • •
2
(D) [CoCl4]2–, [Fe(H2O)6]2+
Rearrangement dsp hybridization
Sol.(B) Same magnetic moment = same number of
Ex.13 [Ni(CN)4]2– is diamagnetic while [NiCl4]2– is
umpaired electrons = n(n 2)
paramagnetic, why ?
Sol. In [Ni(CN)4]2– all orbitals ar doubly occupied, wher n = number of unpaired electrons
hence it is diamagnetic while in [NiCl 4] 2–, Co2+ = 3d7, 3 unpaired electrons
tow orbitals are singly occupied, hence it is Cr2+ = 3d4, 4 unpaired electrons
paramagnetic in nature. Mn2+ = 3d5, 5 unpaired electrons
• • • • Fe2+ = 3d6, 4 unpaired electrons
[Ni(Cl)4]2– : • • • •
3
Rearrangement sp hybridization
Ex.18 The colour of Hg2Cl 2 changes from white to
black when treated with NH3. Why ?
Ex.14 Consider the following complexes –
Sol. Hg2Cl2 reacts with NH3 to give black complex.
(i) K2PtCl 6 (ii) PtCl4.2NH3
Hg2Cl2 + 2NH4OH – Hg + Hg(NH2)Cl + NH4Cl + 2H2O
(iii) PtCl4.3NH3 (iv) PtCl4.5NH3
(Black)
Ex.19 Write the formula of the following complexes.
(i) Pentamminechlorocobalt (III) ion
(ii) Lithium tetrahydridoaluminate (III)
Sol. (i) [Co(NH3)5Cl]2+ ; (ii) Li[AlH4]