Coordination

Compounds

9.1 Werner's Th.ary

Compounds
of Coordination 9.4
9.5
Isomerism In Coordination Compounds
Bonding In Coordination Compounds
J
9.2 o.finitlon of Some Important Terms 9.6 Bonding In Metal Carbonyts
Pertaining to Coordination Compounds
9.7 Importance and Applications of
9.3 Nomenclature of Coordination Compounds Coordination Compounds

Topicwise Analysis of Last 10 Years' CBSE Board Questions (2020-2011)

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9.1 9.2 9.3 9.4 9.5 9.6 9.7

Topic--+

.. Maximum total weightage is of Bonding in .. Maximum SA and LA I type questions

Coordination Compounds. were asked from Bonding in Coordination
Compounds.
.. Maximum VSA type questions were asked from
Isomerism in Coordination Compounds.

------------1( QUICK RECAP ) 1 - - - - - - - -

C) Werner's coordination theory: - Primary valency : Non directional and
► It explains the nature of bonding in complexes. ionisable. It is equal to the oxidation state
Metals show two different kinds of valencies: of the central metal ion.
 - Secondary valency Directional ► Complex compound : A compound formed
and non-ionisable. It is equal to the by combination of two or more simple
coordination number of the metal. It compounds which retain its identity both
is commonly satisfied by neutral and in solid and solution states is called complex
negatively charged or sometimes by compound.
positively charged ligands.
e.g., K,[Fe(CN),], Potassium ferrocyanide
► The ionisation of the coordination compound
[Cu(NH3) 4 ]S04 , Cupramine sulphate
is written as :
[Co(NH,).JCI, ~ [Co(NH,).J'' + 3c1- C) Some important terms pertaining
NH1 Cl coordination compound :

I
H3N"' .:/NH3
Cl······Co
► Coordination entity : The central metal
atom or ion and ligand taken together is
called coordination entity. It may be positive,
H3N /I ··."'
\
-NH3 negative or neutral.
e.g., [Cu(NH3)4]'', [Fe(CN),J'-, [Ni(CO),]
H1N Cl
[Co(NH3),,ICl3 ► Central atom : The atom or ion with which
Rcpresen1ation ofCoC1 3•6NH 3 complex
according to Werner's theory
definite number of ligands are attached in a
definite geometry is called central atom/ion.
C) Addition compounds : The compounds
Any atom/ion which has high positive charge
formed by combination of two or more
simple compounds are called addition density or vacant orbitals of suitable energy
compou11ds. They are of two types : may be central atom or ion, e.g., transition
metals, lanthanoids. It is Lewis acid (electron

4
Double salt : A compound formed by
combination of two or more simple acceptor).
compounds, which is stable in solid state ► Ligands : Molecules or ions which are bound
only is called double salt. In solution it breaks to the central atom/ion in the coordination
into component ions. entity are called liga11ds. A molecule or ion
e.g., K2SO,•Al2(S04 ),-24H 20; Potash alum which has high negative charge or dipole or
FeSO,-(NH,)2S04-6H20; Mohr's salt lone pair of electrons may be ligands. It is
KCI-MgCl,-6H 20; Carnallite Lewis base (electron donor).
► Classification of ligands :
Ligands

charge

Negative ligands Monodentate : Only one Chelating ligands : A bidentate or polydentate

cw, F", er, NOi, donor site t.g., H20, NH) ligand which forms more than one coordinate
NO,, Off, 0 2• bonds in such a way that a ring is formed.
Bidentate : Two donor sites
CH1-NH 2
Positive ligands t.g., (COO·),, CH1-NH 2 I
NO;, NO', N,H; (Oxala10) I CH,-NH1
CH,-NH 1 (Ethyknt'diaminc)
N•utral ligands (Ethylenediamint>)
Ambidentate ligands: Monodcnlatc ligand which
H,Q, NH,, co, Polydentate: More than contains more than one coordinating atom (or
NH,OH, CH,NH, two donor sites e.g., donor atom).
EDTA (Hexadentate) M+-o·-N=o, M+-SCN. M+-CN
or or or
.✓.o
M+-N;'.' M+-NCS M+-NC
'0"
► Coordination number (C.N.) : The total - Within the coordination sphere the
number of coordinate bonds through which sequence of symbols is, first the metal
the central metal atom or ion is atlached atom followed by anionic ligand then
with ligands is known as coordination neutral ligand finally cationic ligand.
number. Examples : [Ag(CN) 2 J- : C.N. = 2, Ligands of same type are arranged
[Cu(NH 3)4)": C.N. = 4, [Cr(H2O)6)'': C.N. alphabetically.
=6 - Polyatomic ligands are enclosed in
► Coordination sphere: The central atom and parentheses.
the ligands which are directly attached are - The number of cations or anions to be
collectively known as coordination sphere. written in the formula is calculated on the
It is non-ionisable and written enclosed in basis that total positive charge must be
square brackets. The ionisable groups are equal to the total negative charge, as the
written outside the brackets. complex as a whole is electrically neutral.
Example: ► Rules for naming coordination compounds :
- The cation is named first then the anion.
[Cu(NH 3),] SO,~ [Cu(NH,),]'• + SOt
- In naming coordination sphere, ligands
Coordination Jonisablc
sphere group are named first in alphabetical order
followed by metal atom and then
Central metal ion
.···. J oxidation state of metal by a roman

4
....,,ugand
J<,t=[Fe(CN)§l numeral in parentheses.
JI'••· ~ - The complex part is written as one word.
Counter ion J Coordination number
- When the coordination sphere is amomc,
Coordinution sphere
name of central metal ends m -ate.
Coordination polyhedron : The spatial
► Naming of ligands :
arrangement of the ligand atoms which are
- Name of aniontc ligands end in -o.
directly atlached to the central atom defines
a coordination polyhedron about the central
e.g.,er : Chlondo
Neutral ligands (with a few exceptions)
atom, e.g., [(Co(NH3)6)]" is octahedral
retain their names e.g., NH,: Ammine
[Ni(CO),) is tetrahedral. Octahedral is most
- Name of cationic ligands end in - ium.
common coordination polyhedron. e.g., No; : Nitronium
0 Homoleptic and heteroleptic complexes : - Certain ligands are represented by
► Homoleptic complexes : Complexes in abbreviations in parentheses instead
which a metal is bound to only one kind of of their complex structural formulae.
ligands are called homoleptic complexes. e.g., ethylenediamine(en).
e.g., [Co(NH3) 6 J'', [Ti(H2O)6 )''. [Cu(CNJ,]'- - Ambidentate ligands are named by using
► Heteroleptic complexes : Complexes in different names of ligands or by placing
which the central atom is bound to different the symbol of donor atom.
type ofligands are called heteroleptic complexes. e.g., -SCN- (Thiocyanato-S or
e.g., [Co(NH3 ) 4Cl2]. K2[Fe(CN),NO], Thiocyanato), -NCS- (Thiocyanato-N or
[Fe(H 2O)5NO]SO, lsothiocyanato), -ONO- (Nitrito-O or
Nitrito), -NO; (Nitrito-N or Nitro)
0
►
Nomenclature ofcoordination compounds :
Rules for writing the formula of - The prefixes di-, tri-, tetra-, penta-
coordination compounds : and hexa- are used to indicate the
- Formula of the cation whether simple or number of each ligand. If the ligand
complex must be written first, followed name includes such a prefix, the ligand
by anion. name should be placed in parentheses
- The coordination sphere is writlen in and preceded by bis-(2), tris-(3),
square brackets. tetrakis-(4),pentakis-(5) and hexakis-(6).
C) Isomerism : Two or more substances having structural or spatial arrangement are called
the same molecular formula but different isomers and phenomenon is called isomerism.

IIsomerism I
I
+
Structural isomerism
+
Stereoisomerism

Ionisation Hydrate Linkage Coordination

isomerism isomerism isomerism isomerism
Compounds. which give Isomers, which differ \Vhen an ambidentate ligand When both positive and
different ions in solution due in the number of water attached to metal through negative ions of a salt are
to the exchange of ions in molecules attached to different atoms then the complex ions and two isomers
coordination sphere and counter the metal atom or ion as compounds are said to be differ in the distribution of
ions are called ionis,llion ligands are called hydrate linkc,ge isomers. ligands in two complex ions
isomers. isomers. [Co(NO2)(NH,),JCI then the isomers arc called
[CoBr(NH,),JSO,, [Cr(H2O)6 JCI,. (Co(ONO)(NH,),JCI coordination isomers.
[CoSO,(NH,),JBr JCr(H20),CIJCl,-H2O [Co(NH,),!ICr(CN),(,
[Co(CN),JICr(NH,),1
IStereoisomerisml
I
f
•Geometrical or cu-trans isomerism Optical ilomttism
If two identical ligands occupy This isomerism arises due to non-
adjacent positions ⇒ cis superimposable mirror images.
+

4
If occupy opposite positions ⇒ trans
I Only in octahedral complexes with 2 or 3
+
In square Planar
+
In octahedral
bidentatf ligands.

Shown by Shown by +
cis
t
trans
I
+ + + (optically active) (optically inactive)
MA 2 X2 MA,X, MA,X, I
MABX, .------'-t + +
MA 2 XY
MABXY
cis trans
+
I d-form

+
I-form

If all three similar groups

If three similar groups are
occupy adjacent position then present around meridian of
Jae-isomer octahedra then mer-isomer
(• Geometrical isomerism is not shown by tetrahedral complexes.)

C) Bonding in coordination compounds : - Central metal ion can use appropriate

► Valence bond theory : It was developed by number of s, p or d-orbitals for
Pauling. hybridisation depending upon the total
number of ligands.
- A suitable number of vacant orbitals
- The outer orbital (high spin) or inner
must be present in the central metal atom
orbital (low spin) complexes are formed
or ion for the formation of coordinate depending upon whether outer d-orbitals
bonds with the ligands. or inner d-orbitals are used.
Typeof
C-No.
hybridisation
Geometry Examples
I
~
2 sp Linear
- _lAg(NH,i,r. !Ag<cNJ,r I
~
3 sp' Trigonal planar (HgI,r I
 Ni(CO),, [NiX,]'-, [ZnCI,J'-, [CuX,]'-.
sp' Tetrahedral
where, X =er.Br-, 1-
4 -
dsp' [Ni(CNJ,]'-, [Cu(NH3),]'', [Ni(NH,l,]''
I
Square planar
-
dsp' Trigonal bipyramidal [Fe(C0)5 ], [CuCI,]'-
5 I-
sp'd Square pyramidal [SbF,]'-
- ~ -
d'sp' I Octahedral (Inner orbital) [Cr(NH3).J''. [Fe(CN)6['-
6
L__
sp'd' I Octahedral (Outer orbital) [FeF,]'-, [Fe(H20)6]''. [Ni(NH,),l''
I
Inner orbital complexes I Outer orbital complexes
[ Involves inner d-orbitals i.e., (n - l)d-orbitals. Involves outer d-orbitals i.e., nd-orbitals.
-
Low spin complexes High spin complexes
Have less or no unpaired electrons. Have large number of unpaired electrons.
e.g., [Co(NH3 ) 6 j 3', [Co(CN)6 J'- Ie.g., [MnF6]'-. [CoF6]'-
Low spin complexes are generally electrons will remain unpaired and a
diamagnetic and high spin complexes are high spin complex is formed.
paramagnetic. If t:., > P, then pairing of electrons takes
- Paramagnetism oc No. of unpaired electrons. place and a low spin complex is formed.
- Crystal field splitting in tetrahedral
- Magnetic moment = Jn(n+2) B.M.
complexes is shown as :
where n = number of unpaired electrons.

4
d.,,.d,-:-dc:
Crystal field theory : It assumes the
ligands to be point charges and there is
electrostatic force of attraction between
ligands and metal atom or ion. When
ligands approach the central metal ion,
then the five degenerate orbitals do not
possess equal energy any more and results d,, ,:,d,,
AveragCC'l'll.'1¥)'
in splitting. which depends upon nature of d-orbitals or1hed-orbitals Splmmgof
inasphi..•ncal d-orbi1ahi11
ligand field strength. in free tOn
cryi.1al field tctrahcdnl
- Greater the ease with which the ligand crys.tal field.

can approach the metal ion, the greater - Difference in energy between e and r,
will be the crystal field splitting caused by it. level is less in tetrahedral complexes.
- Crystal field splitting in octahedral 4
coordination complexes is shown as : t:., = 960
dA: J~' d:1 - Spectrochemical series : Arrangement
of ligands in the order of increasing field
strength.
Weak field Increasing order of CFSE (~0 ) Strong fidd
ligands ligands
'-1=====11:z.x r- <Br-<SCW<CJ-<S2-<F-<Off<C,O~-<H,O
dn~ d1:• d{:
Average energy <NCS- <edta4-<NH,<en<N0i<CN-<C0
d-orbitals of the d-orbitals Splitting of
in a spherical d-orbilals in
in free ion
crystul field an octahedral
crystal field.
0 Colour of coordination compounds : The
magnitude of CFSE (60 ) for most of the
- If 6 0 < P (where 'P' is energy required complexes is of the same order as the energy
for forced pairing of electrons) then the of a photon of visible light. Hence, whenever
 d-d transition takes place, it imparts colour
to the complex. The colour of the complex is
the colour complementary to the wavelength
absorbed.
C) Bonding in metal carbonyls : Filled metal Empty n•lp M-->C n-bond
d-orbital orbital of CO
► Metal-carbon bond in metal carbonyls
possesses both cr- and 1t-characters. C) Applications of coordination compounds :
► Its formation involves the following steps : ► Coordination compounds are of great
- Overlap of filled n,, orbital of CO with importance in biological system. e.g.,
suitable empty metal d-orbital resulting chlorophyll, haemoglobin, vitamin B12, etc.
in the formation of sigma bond. are coordinate compounds of Mg, Fe and Co
E:>M<D + ©>C::O: - respectively.
Vacant metal Orbital cont.iining
orbital lone pair ► Coordination compounds are used for
E:>M©C::O: qualitative and quantitative analysis,
M+-Co-bond extraction of metals, electroplating,
- !t-overlap involving filled metal d-orbital photography and as dyes.
with an empty antibonding n· 2p orbital ► cis-Platin is used in cancer treatment, EDTA
of same CO. This results in formation of is often used for treatment oflead poisoning.
M ➔ C 1t-bond. This is also called back ► Coordination compounds are also used as
bonding. catalyst.
 9.1 Werner's Theory of (b) Both Assertion (A) and Reason (R) are
correct statements, but Reason (R) is not
Coordination Compounds the correct explanation of the Assertion
!IWlllpmark) (A).
(c) Assertion (A) is correct, but Reason (R)
I. One mole of CrCI, •6H1O compound reacts
is incorrect statement.
with excess AgNO, solution to yield two
(d) Assertion (A) is incorrect, but Reason
moles of AgC~•>· The structural formula of
(R) is correct statement. (2020)
the compound is
(a) [Cr(H,0)5CI] Cl,· H 2O 7. Write the coordination number and
(b) [Cr(H2O),Cl3 ] • 3H,O oxidation state of platinum in the complex
(c) [Cr(H,O),Cl,]Cl·2H2O (Pt(enl,Cl2 ]. (2018)
(d) [Cr(H,O)6Cl,l (2020) 8. Which of the following is more stable
2. When a coordination compound CrCl,·6H,O complex and why?

4
is mixed with AgNO,, 2 moles of AgCI are (Co(NH,)6]'' and [Co(en),]'' (Delhi 2014)
precipitated per mole of the compound. 9. What do you understand by 'denticity of a
Write structural formula of the complex. ligand'? (Foreign 2011)
(AI 2019, 112, Delhi 2016)
~ 3. What is the difference between a complex
and a double salt? (Al 2019)
E'tl (2 marks)
IO. Explain the following terms giving a suitable
, 4. When a coordination compound CoCl,•6NH, example in each case:
is mixed with AgNO,, 3 moles of AgCI are (i) Ambidenate ligand
precipitated per mole of the compound. (ii) Denticity of a ligand (2/3, Al 2011)
Write structural formula of the complex.
(112, Al 2016) 9.3 Nomenclature of Coordination
Compounds
9.2 Definition of Some Important
Terms Pertaining to
IIWl1I (1 mark) _ _
1I. Write the formula of the following
Coordination Compounds coordination compound :
IIWl'II (1 mark) _ _ Iron (III) hexacyanidoferrate(II) (l/3, 2018)
5. The coordination number of 'Co' in the 12. Write the IUPAC name of the following
complex (Co(en),)'• is complex: [Cr(NH,),CI,]. (113, Delhi 2017)
(a) 3 (b) 6 13. Write the IUPAC name of the following
(c) 4 (d) 5 (2020) complex: [Co(NH,)5(CO,)]CI.
6. Assertion (A): [Pt(en),Cl2]'' complex is less (113, Delhi 2017)
stable than [Pt(NH3),Ct,]'• complex. 14. When a coordination compound CrCl,·6H O
2
Reason (R) : [Pt(en),Cl2]'' complex shows is mixed with AgNO,, 2 moles of AgCI are
chelate effect. precipitated per mole of the compound.
(a) Both Assertion (A) and Reason (R) are Write IUPAC name of the complex.
correct statements, and Reason (R) is (l/2, Delhi 2016)
the correct explanation of the Assertion 15. Write the IUPAC name of the complex
(A). [Cr(NH,),Cl,]CI. (1/3, Al 2014)
16. Write down the formula of: 27. Using IUPAC norms write the formulae for
Tetrammineaquachloridocobalt(lll)chloride. the following coordination compounds :
(Al 20/2C) (i) Hexaamminecobalt(III) chloride
17. Name the foUowing coordination compound: (ii) Potassium tetrachloridonickelate(ll)
K,[CrF6 ). (Foreign 201 I) (Al 2015)

18. Write the IUPAC name of 28. (i) Write down the IUPAC name of the
[PtCl(NH 2CH,)(NH,)2)Cl. (Delhi 201 IC) following complex: [Cr (en),]Cl 3.
(ii) Write the formula for the following complex:
19. Write the IUPAC name of [Pt(NH,),Cl 2 )Cl 2.
Potassium trioxalatochromate (111).
(Al 201 IC)
(Foreign 2015)
20. Write the IUPAC name of
29. Name the following coordination compounds
(Cr(NH3 ) 6 ][Co(CN)6 ). (Al 201 IC)
and draw their structures :
(i) (CoC12 (en),]CI
11111£1111 (2 marks) (ii) (Pt(NH,),Cl(NO2))
21. Give the formulae of the following (At. No. Co= 27, Pt= 78)
compounds: (Foreign 2011)
(a) Potassium tetrahydroxidozincate(II) ~(3marks)
(b) Hexaammineplatinum(IV) chloride
(2020) 30. Write the IUPAC name of the following :
(i) [Co(NH,)6 ]CI, (ii) [NiCl,J'·
22. Using IUPAC norms write the formulae for
(iii) K,(Fe(CN)6 ] (Al 2015C)
the following :
(i) Pentaamminenitrito-O -cobalt(III) 31. Write down the IUPAC name for each of the
chloride following complexes :
(ii) Potassium tetracyanidonickelate(ll) (i) [Co(NH,),Cl]Cl2 (ii) K,(Fe(CN)6 )
(Delhi 2019) (iii) (NiCl4 ] 2 • (Delhi 2014C)
32. Write the IUPAC name and draw the
Using IUPAC norms write the formulae for
the foUowing : structure of each of the following complex
entities:
(a) Sodium dicyanidoaurate(I)
(b) Tetraamminechloridonitrito-N-platinum(IV) [ 0 (coo1]3- (ii) [Cr(CO)6]
sulphate (Al 2017) (i) ( 200}3
24. Using IUPAC norms write the formulae for (iii) [PtCl,(C2H,)]"
the following : (At. nos. Cr = 25, Co = 27, Pt = 78)
(a) Tris( ethane-1,2,diamine)chromium(III) (Al 2014C)
chloride
33. Write the IUPAC names of the following
(b) Potassium tetrahydroxozincate(ll) coordination compounds:
(Al 2017)
(i) (Cr(NH 3),Cl3 )
25. Using IUPAC norms write the formulae for (ii) K3[Fe(CN)6 ]
the following : (iii) [CoBr2(en),]', (en= ethylenediamine)
(a) Potassium trioxalatoaluminate(III) (Delhi 2013)
(b) Dichloridobis(ethane-1 ,2-diamine)
cobalt(III) (Al 2017) 9.4 Isomerism in Coordination
26. (i) Write down the IUPAC name of the Compounds
following complex :
(Cr(NH3),Cl2(en)]Cl(en=ethylenediamine)
lll'lifi.1II (1 mark)
(ii) Write the formula forthe following complex: 34. Assertion (A) : Linkage isomerism arises
Pentaamminenitrito-O-cobalt (111). in coordination compounds because of
(Delhi 2015) ambidentate ligand.
 Reason (R) : Ambidentate ligand like NO, 46. What type of isomerism is exhibited by the
has two different donor atoms i.e., N and 0. following complex :
(a) Both Assertion (A) and Reason (R) are [Co(NH,),SO,]CI (Foreign 2014)
correct statements, and Reason (R) is 47. What type of isomerism is exhibited by the
the correct explanation of the Assertion complex (Co(NH,J,NO,)"? (Foreign 2014)
(A). 48. Indicate the types of isomerism exhibited
(b) Both Assertion (A) and Reason (R) are by the complex (Co(NH,),(NO,))(NO,),.
correct statements, but Reason (R) is not (At no. Co= 27) (Al 2012C)
the correct explanation of the Assertion
49. Give IUPAC name of ionisation isomer of
(A). (Ni(NH1) 1N0 3 )CI. (Al 2012C)
(c) Assertion (A) is correct, but Reason (R)
is incorrect statement. --(2marks)
(d) Assertion (A) is incorrect, but Reason 50. Write IUPAC name of the complex
(R) is correct statement. (2020) (Cr(NH,) 4Cl 2]'. Draw structures of
35. What type of isomerism is shown by the geometrical isomers for this complex.
complex [Co(en), Cl,)"? Name the structure (Delhi 2019)
of an isomer of this complex which is 51. Draw the structure of isomers, if any and
optically active. (112, 2020) write the name of the following complexes:

4
36. What type of isomerism is exhibited by the (i) (Cr(NH,),CJ,J•
complex [Co(NH,),Cl)S04 ? (113, 2018) (ii) (Co(en),]'' (Foreign 2011)
37. What type of isomerism is shown by the
~(3marks)

-
complex [Co(NH,)6 )[Cr(CN)6 )?
52. Indicate the types of isomerism exhibited by
(113, Delhi 2017, Foreign 2014) the following complexes :
38. What type of isomerism is shown by the (i) (Co(NH,),(NO,))'•
complex [Co(en),)Cl,? (113, Delhi 2017) (ii) (Co(enl,)CI, (en= ethylene diamine)
39. What type of isomerism is shown by the (iii) (Pt(NH,),CI,) (Delhi 2015C)
complex (Co(NH,),(SCN))"? 53. Write the IUPAC name of the complex
(113, Al 2017) [Cr(NH1 ) 4Cl2 )'. What type of isomerism
40. Draw one of the geometrical isomers of the
does it exhibit? (Delhi 2014)
complex (Pt(en),Cl 2)'' which is optically 54. Draw the structures of optical isomers of
active. (113, Delhi 2016) each of the following complex ions :
(Cr(C,O,))'·, [PtO,(en),]", (Cr(NH3l,Cl2(t11)]·
41. Draw one of the geometrical isomers of the
complex (Pt(e11)2Cl2)" which is optically (Delhi 2014C)
inactive. (Al 2016) 55. Write the types of isomerism exhibited by
the following complexes :
42. Draw the geometrical isomers of complex
(i) (Co(NH,),Cl)S04
(Pt(NH,),CI,]. (l/3, Delhi 2015)
(ii) (Co(enl,)''
43. Write down the IUPAC name of the complex
(iii) (Co(NH,)6 ) (Cr(CN)6 ) (Delhi 2013)
(Pt(e11),Cl 2)'•. What type of isomerism is
56. Name the following coordination entities and
shown by this complex? (Al 2015)
draw the structures of their stereoisomers :
44. Draw the geometrical isomers of complex (i) (Co(en},Cl2)' (en= ethane-1,2-diamine}
(Pt(en),Cl,)'•. ( 113, Foreign 2015) (ii) (Cr(C,04 ),]'·
45. What type of isomerism is exhibited by (iii) (Co(NH,),CI,)
the complex [Co(en),]'•? (en = ethane-1,2- (Atomic numbers Cr= 24, Co= 27)
diamine) (113, Al 2014) (Al 2012)
57. Write the structures and names of all the 67. (a) Why is (NiCl,]'- paramagnetic while
stereoisomers of the following compounds : (Ni(CNJ,]'- is diamagnetic?
(i) [Co(enl,]CI, (ii) (Pt(NH,) 2Cl2 ] (Atomic number of Ni = 28)
(iii) [Fe(NH3),Cl2]CI (AI 2011) (b) Why are low spin tetrahedral complexes
rarely observed? (2/3, AI 2017)
9.5 Bonding in Coordination
68. For the complex [Fe(CN)6 J3-, write the
Compounds hybridization type, magnetic character and
spin nature of the complex.
K'J:Q lc1ma~ --
(At. number: Fe= 26). (2/3, Delhi 2016)
58. The crystal field splitting energy for
69. For the complex [Fe(H,0)6)3', write the
octahedral (t.,,) and tetrahedral (A,)
complexes is related as hybridization, magnetic character and spin
2 5 of the complex. (At. number Fe= 26)
(a) A,= 6 0 (b) A,= A0 (2/3,Al 2016)
9 9
70. (i) On the basis of crystal field theory, write
(c) AI = iA0 (d) A,= 2 Ao (2020)
9 the electronic configuration of ti' ion
59. Write the IUPAC name and hybridisation if A,< P.

4
of the complex [CoF6]'- (Given : Atomic (ii) Write the hybridization and magnetic
number of Co= 27) (l/2, 2020) behaviour of the complex [Ni(CO)4J.
60. Write the hybridisation and number of (At. no. of Ni =28) (213, Delhi 2015)
unpaired electrons in the complex [CoF6]'-.
(113, 2018) 71. Write the hybridization and shape of the
(Atomic no. of Co= 27)
following complexes :
Why a solution of [Ni(H 2O)6)'' is green
(i) [CoF6 ]'- (ii) (Ni(CN),J 2 -
while a solution of [Ni(CNJ,]'- is colourless?
(At. no. of Ni= 28) (J/3, Delhi 2017) (Atomic number: Co= 27, Ni= 28)
(Al 2015)
62. Write the hybridisation and magnetic
character of [Co(C,O4),]'-. 72. Write the state of hybridization, shape and
(At. no. of Co= 27) (113, Delhi 2017) IUPAC name of the complex [CoF6]'-.
63. Why is [NiCI,]'- paramagnetic but (Ni(CO),] (Atomic no. of Co= 27) (Foreign 2014)
is diamagnetic? (At. no. : Cr = 24, Co = 27, 73. Write the state of hybridization, shape and
Ni= 28) (1/3, Al 2014) IUPAC name of the complex (Ni(CN)4)'-.
64. Explain the following term giving a suitable (Atomic no. of Ni= 28) (Foreign 2014)
example: 74. Write the state of hybridization, shape and
Crystal field splitting in an octahedral field.
IUPAC name of the complex [Co(NH3)6]''.
( 1/3, Al 201 I)
(Atomic no. of Co= 27) (Foreign 2014)
EW!2ma rks)
75. Give the formula of each of the following
65. Write IUPAC name and hybridization of the coordination entities:
following complexes :
(i) Co'• ion is bound to one Cl-, one NH,
(i) [Ni(CO),] (ii) [CoF6]'-
molecule and two bidentate ethylene
(Atomic number Ni = 28, Co= 27) (2020)
diamine (en) molecules.
66. Out of [CoF6 ]'- and [Co(C 2O 4 J,]'-. which
(ii) Ni'• ion is bound to two water molecules
one complex is
(i) diamagnetic (ii) more stable and two oxalate ions.
(iii) outer orbital complex and Write the name and magnetic behaviour of
(iv) low spin complex? each of the above coordination entities.
(Atomic no. of Co= 27) (Dellri 2019) (At. nos. Co= 27, Ni= 28) (213, Delhi 2012)
76. State a reason for each of the following 85. Name the following coordination entities
situations: and describe their structures.
(i) Co" is easily oxidised to Co'' in (i) IFe(CN)6 J'-
presence of a strong ligand. (ii) ICr(NH 3),Cl2)'
(ii) The molecular shape of Ni(CO), is not (iii) !Ni(CNJ,)'- (AI 2012)
the same as that of INi(CN),)'-. 86. Write the name, stereochemistry and
(213, Delhi 2012) magnetic behaviour of the following:
77. Using valence bond theory, explain the (At. nos. Mn= 25, Co= 27, Ni= 28)
geometry and magnetic behaviour of (i) K,1Mn(CN) 6 )
ICo(NH 3) 6 )". (ii) ICo(NH 3 )sCl)Cl2
(At. no. of Co= 27) (2/3, Delhi 2012C) (iii) K,INi(CN),j (Delhi 201 I)
78. Using valence bond theory of complexes, 87. For the complex [Fe(en),Cl2]CI, identify the
explain the geometry and magnetic nature of following:
INi(CN),)'-. (At. no. of Ni= 28) (i) Oxidation number of iron
(2/3, Delhi 20 I2C) (ii) Hybrid orbitals and shape of the
complex
79. IFe(H 2O)6]'• is strongly paramagnetic
whereas !Fe(CN),]'- is weakly paramagnetic. (iii) Magnetic behaviour of the complex
(iv) Number of its geometrical isomers

4
Explain (At. no. Fe= 26) (Delhi 20I2C)
(v) Whether there may be optical isomer
80. Give the name, the stereochemistry and also.
the magnetic behaviour of the following (vi) Name of the complex. (Delhi 2011)
complexes:
(i) (Co(NH 3) 5Cl)Cl, 88. Write the state of hybridization, the shape
(ii) K2(Ni(CN),1 (Foreign 201 I) and the magnetic behaviour of the following
complex entities :
IIEIJIII (3 marks) (i) !Cr(NH3 ),Cl2)Cl
(ii) ICo(en),)Cl3
81. Write the hybridisation and magnetic
(iii) K,INi(CN),I (AI 201 I)
character of the following complexes:
(i) IFe(H 2O)6 )" (ii) [Ni(CNJ,]'-
9.6 Bonding in Metal Carbonyls
!Atomic number: Fe= 26, Ni = 28)
(Al 2019) ~(lmark)
82. For the complex INiCl,) 2-, write 89. Out of NH, and CO, which ligand forms a
(i) the IUPAC name more stable complex with a transition metal
(ii) the hybridization type and why? (113, Al 2015)
(iii) the shape of the complex. 90. State a reason for the following situation :
(Atomic no. of Ni= 28) (AI 2013) CO is a stronger complexing reagent than
83. What is meant by crystal field splitting NH,. (I/3, Delhi 2012)
energy? On the basis of crystal field theory, 91. Why is CO a stronger ligand than c1-1
write the electronic configuration of d' in (Foreig11 201 I)
terms of 121 and e1 in an octahedral field when
(i) 6.. > p 9.7 Importance and Applications
(ii) 6.. < P (Al 2013) of Coordination Compounds
84. Write the name, the structure and the
~(lmark)
magnetic behaviour of each one of the
following complexes : 92. Give two examples of coordination
(i) [Pt(NH3) 2Cl(NO2)] compounds used in industries.
(ii) (Co(NH,),Cl,)CI (iii) Ni(CO), ( 1/3, Delhi 2012C)
(At. nos. Co= 27, Ni = 28, Pt= 78) 93. Give names of two complexes which are used
(Delhi 2012) in medicines. (113, Delhi 2012C)
l. For one mole of the compound, two moles
17. Potassium hexafluoridochromate(III).
of AgCI are precipitated which indicates two
ionisable chloride ions in the complex. Hence, its 18. Diamminechlorido(methylamine)platin
um(I I)
struc tura l formula is [CrCl(H 0) ]Cl ·H,O chloride.
2 5 2
2. Refer to answer 19. Tetraamminedichloridoplatinum(IV) chlor
I.

ide.
3. Double salts dissociate into ions completely 20. Hexaamminechromium(III)
when dissolved in water. On the othe r hand , in hexacyanidocobaltate(lll).
complexes, the complex ion does not dissociate.
21. (a) K2 [Zn( OH) ,]
4. Structural form ula: [Co( NH ) ]Cl Potassium tetrahydroxidozincate(ll)
3 6 3
5. (b): Etha ne-I , 2-diamine (en) is a bidendat (b) [Pt( NH3) 6]CI,
e
ligand. Hexaammincplatinum(IV) chlor ide
6. (d): Formation of chelate rings increases the 22. (i) [Co(NH3 ) 5(0N O)]C l
2
stability of the complex.
(ii) K2 [Ni(CN),]
7. Coordination number and oxidation state
23. (a) Na[Au(CN),]
of Pt in the complex [Pt(e11l,Cl ] are 6 and +2
2 Sodium dicyanidoauratt(l)
because en is a bidentate and neutral ligand.
[Pt(NH 3).(C l)(N 02)]SO,

E.;;;;~;;;;
(b)

8. [Co (enl ,]'' is mor e stable complex than

Tet.raamminechloridonitrito•N•platinum(IV) sulph
ate
24. (a) [Cr(en)3]Cl3
Tris(etham•-1,2-diimine)chromium(III) chloride
(b) K2 [Zn(OH),]
Potassium tetrahydroxidozincate(II)
For example, bidentate ligand etha ne-I , 2-diamin
e 25. (a) K3[Al(C20,l, ]
has two dono r nitrogen atoms which can link to
central metal atom. Potassium trioxalatoaluminatt(III)

Hif ~-C Hi- CH cNH (b) [CoCl,(en),]•

2 Oichloridobis(ethane-1,2-diaminc)cobah(111) ion
Ethane- I, 2-diamine
10. (i) Ambidcntate ligand: A unidentate ligan 26. (i) Dia mm ined ichl orid o(et han e-1, 2-
d
which cancoordinate to central metalatom through diamine) chromium(III) chloride.
two different atoms is called ambidentate ligand. (ii) [Co(NH3)s(O NO) ]''
For example, NO, ion can coordinate eithe (i) [Co(NH3) 6 ]Cl3
r 27.

2[NiCl,1
thro ugh nitrogen or through oxygen to the (ii) K

central metal atom/ion. 28. (i) Tris (eth ylen edia mmi ne)c hrom ium (JII)
(ii) Refer to answer 9. chloride
11. Fe,[Fe(CN)6l, (ii) K3[Cr(oxl,]
12. IUP ACn ame ofth ecom plex [Cr( NH, 29. (i) Dichloridobis (eth ane- I, 2-diamine)
l,Cl 3] is
triamminetrichloridochromium(III). cobalt(III) chloride.
13. Pentaamminecarbonatocobalt(111) chloride
14. IUPAC nam e of the complex
[CrCl(H 20).] Cl2-H20 is:
pentaaquachloridochromium (111) chloride.
15. IUPAC name of the complex [Cr(NH ) Cl
3 4 2]CI t:~In~·
(..1.'\jn
enJ
n ;···'.n~·
: <I.. [ en
. .... .~
~
is tctraamminedichloridochromium(111) chloride. Cl
Octahedral Octahedral
16. [Co(NH,l.(H,O)(Cl)]Cl2 cis-(CoCt,(,n>,r lrans-(CoCl 2(tnl,l •
 (ii) Diamminechloridonitrito-N-platinum(Jl) 38. The complex, [Co(en)3]Cl3 shows optical
isomerism.
H3N'\_ /Cl
39. The complex [Co(NH 3)s(SCN)[" shows
Pt
linkage isomerism as SCN· is an ambidentate ligand.
H3N/ '\_N02
40. cis-isomer of the complex (Pt(en),Cl2[ 2' is
30. (i) Hexaamminecobalt(lll) chloride
optically active.
(ii) Tetrachloridonickelate(JJ) ion CI 72+

~Ptj·:7f
(iii) Potassium hexacyanidoferrate(III)
31. (i) Pentaamminechloridocobalt(lll) chloride
I
en : •
(ii)
(iii)
Refer to answer 30(iii).
Refer to answer 30(ii).
~-t)
32. (i) Trioxalatocobaltate(lll) 41. Trans-isomer is optically inactive due to the
ox
0· 7 r
Of: _Co •
presence of plane of symmetry.

Cl =-t
v.-lJ
·~
4
(ii) Hexacarbonylchromium(0)

oc co
I co Cl
'-er/ 42. Geometrical isomers
oc/1 '-co
co Cl:"\·. 7 NH3
C \ .. 7 : NH3
Trichloridoetheneplatinum(JJI) ! Pt ,: : Pt
H'-. .,,,,,H
C
-rI
,"Cl
C l / .. \_:'NH3 H3N/ .. \..:Cl
cis-Diamminedichlorido lra,u-Diamminedichlorido
11 -- P;-c, platinum(II) platinum(II)
C I
H..,... ••,,,,H !1 43. JUPAC name - Dichloridobis(ethane-1,2·
33. (i) Triamminetrichloridochromium(lll) diamine)platinum(JV) ion. This complex shows
(ii) Refer to answser 30(iii) geometrical and optical isomerism.
(iii) Dibromidobis(ethane-1,2-diamine)
Cl 72+ Cl 72+
cobalt(lll) ion
34. (a) /;,,J·:,?:\
en : Pt , en en :
~(;;--p
Pt
~ti~ ~-t)
1

35. (CoC1 2(en) 2]• Dichloridobis(ethane-1,

2-diamine)cobalt(III) ion
This complex exhibit both optical and geometrical
tram cis
isomerism and cis isomer is optically active.
Cl
, _ I .,,.._
et,,,Co._,_yi
ti
7' en
\ 'co(Cl
(
Cl
7'

;J
Cl"
Cl
/c
<
(en

Len
7'
cis-isomer is opticaUy active.

~t;;f'
Cl 12+,
~J/½r·
! c,,'.. Pt ,• en
trans1orm
ci.r-form exists in en V : Pt"-._ : ;
two cnantiomcric fonns
(dand/) V ... {-~ : <)V
en
36. Ionisation isomerism: (Co(NH3 ) 5Cl]SO4 and dextro Mirror en /aevo
(Co(NH 3 ) 5SO,)Cl
37. Coordination isomerism 44. Refer to answer 43.
45. Optical isomerism :

r"l
""'--c ./'),,
<;;;J°"-5
73• I eh'c~
r,v•

\..,/L,;,,
Al·7CI
e11:
Cl

Pt :
72+

Clt,dA
Cl

: Pt : en
72+

dextro Mirror /a,vo

V.1.\
Leu
(j.V
en
Trls(cthane• l. 2-diamine) Tris(dhane-1, 2-diamine)
cobalt(lll)ion cobah(l11) ion Mirror
dextro lm:vo
46. Refer to answer 36. [Cr{NH,),Cl2{en))':
47. Linkage isomerism : [Co{NH,l,N02 )" and
[Co{ONO)(NH,},) 2'
48. {i) Ionisation isomers :
[Co{NH,)s(N02))(NO,>, and
[Co{NH,ls(NO,))(N02)(NO,)
(ii) Linkage isomers : [Co(NH,),(N0 2))(N03 ),
and [Co{NH,)5 (0NO))(NO,),
49. Ionisation isomer of [Ni(NH1),N01]CI 55. {i) Refer to answer 36.
is [Ni(NH,),Cl)NO,. The IUPAC name of this (ii) Refer to answer 45.
complex is triamminechloridonickel(ll) nitrate. (iii) Refer to answer 37.
50. Tetraamminedichloridochromium(III) ion 56. {i) Refer to answer 35.

4
Geometrical isomers of [Cr(NH,) 4Cl2 )';
(ii) [Cr(C,O,>,)'- : Trioxalatochromate(III) ion
Cl 7• Cl 7• It will show optical isomerism.
H37'\J/cl H37•,:J·7NH3 Refer to answer 54.
: Cr : : Cr : (iii) (Co{NH,),CI,] : Triamminetrichloridocobalt{Ill)
HJ J/..t:J
I NH3 H3Y--f :JNH3
It will ex.isl in two geometrical isomeric forms :
NH3 NH3
Cl
cis-Tttraamminedichlorido tra,u-Tdraamminedichlorido tt3N, I ,,..c1
chromium(UI) ion chromium(JJI) ion Co
c1/ I '-c1
51. (i) Refer to answer 50. NH3
(ii) Refer to answer 45. Facial (fac) Meridional (mtr)
52. (i) Refer to answer 47. 57. (i) tris(ethane-1,2-diamin c) cobalt(III)
(ii) Refer to answer 45.
chloride: Refer to answer 45.
(iii) Refer to answer 42.
(ii) Refer to answer 42.
53. Refer to answer 50. (iii) (Fe{NH,),Cl2 )CI
54. [Cr(C20,))'-:

AtJJ- oxl 73- H37._J.

NH3 7+
c1 I
Cl
H3~ .. ·~·/H3
:r
ox: Cr :
~\' 7\
: Cr : ox :
7
Fe : /'\e :
v..l\ ox
VJ~
ox
H3Y-f{1
NH3
H3 N/.f :JNH3
Cl
(Cr(oxl,I'- Mirror (Cr(ox),11 - cis-tetraamminedichlorido trans-tetraamminedichlorido
dextro /aevo Iron (Ill) Iron (Ill)
[PtCl2 (en) 2 ] 2
' : 58. (c)
59. The IUPAC name of [CoF6)'- is J,I 4s 4p
hexafluoridocobaltate(III). [Ni(CO),) 1111111111111111 B EEE
Oxidation state of Co ion in [CoF6)'- is +3. sp3 hybridisation
Jd 4s 4P 4d
(t<lrahedral)
four electrons
Co'':! 11 It It It It II JITO~I~I_._I--'-..__. donated by four
Co" in [CoF.)'- : CO ligands
(strong ligand)
Jd 4s .--.-Z-, 4d
jnj t It It I ti B~Hxxj I The complex has all paired electrons hence, it is
diamagnetic .
.tpld2hybridisa1ion
six pairs or ch.-ctrons 64. The splitting of the degenerate d-orbitals
from six t.._k>n into three orbitals of lower energy, 1,, set and two
(Weak ligands )
orbitals ofhigher energye, set due to the interaction
No. of unpaired electrons = 4 of ligand in an octahedral crystal field is known
60. Refer to answer 59. as crystal field splitting in an octahedral field.
61. [Ni(H,O)6 ] 2' is a high spin complex d,, - >"· d,,
(6, small) while [Ni(CN),]'- is a low spin square
/2-
4
planar complex. t /_IJ/St.}D"
In [Ni(H 20)6 ] 2' complex, d-d transitions are Energy I Average cncrg~ 2/56, •
1
taking place on absorbing low energy radiation ~ of the d-orbitals d d d "
d-orbitals in in a spherical .r,• >":' r:
(red component of spectrum) from visible region fTcc metal ion crystal field
showing green as the complementary colour.
d-orbital splitting in an oc1ahcdral crySlal field
ln [Ni(CN),] 2- complex, d-d transitions do not
[Mn(H 2O)6 )" contains: Mn" - 3d' configuration,
take place because there is no unpaired electron
C.N. = 6, octahedral structure, H 20 ( weak field
present hence, complex is colourless.
ligand) hence t.. < P.
62. The complex [Co(C,O,),]'- has d'sp'- 11e:
hybridisation and it is diamagnetic in nature due 11111< '
to the absence of unpaired electrons. degenerate ! ! ! I'
d-orbitals_ in Wtak OC:!hedral
63. [NiC~[2- contains Ni2' ion with 3d'configuration. free metal ion. ligand field
Jd 4s 4p
Electrons enter into e1 orbital before pairing. It has
Ni'' ln1111111 ! It I □ I T O
Ground state five unpaired electrons.
Cl- is a weak field ligand. Hence, outer 4s and [Mn(CN)6 )'· contains: Mn2' ion-3d' configuration,
4p-orbitals are used in hybridisation. C.N. = 6, octahedral geometry, CN- (strong field
Jd 4s 4p ligand) hence, t.0 > P.
[NiCl,]'- !HIHl111 t It I El~ 11111<--e,
h4 nd
CI liga ~ sl hybridisation.
----- !!!HI t..,> p
wil
(tctrah<dral)
,,
4 electron pairs donated Hence, pairing of electrons in t,, orbitals takes
br 4Cr ligands place. It has only one unpaired electron.
(weak ligand)
It has two unpaired electrons hence, it is 65. (i) Name; Tetracarbonylnickcl (0)
paramagnetic. For hybridisation; Refer to answer 63.
[Ni(CO),l contains Ni(0) - 3d"4s' configuration. (ii) Refer to answer 59.
. Jd 4s 4p 66. Formation of (CoF6]'- and (Co(C,O,),]'-
Nt(O)
Ground stale
I11 I11 I11 I 1 I t ! [ill I T O can be represented as :
Jd
CO is a strong field ligand hence, 4s-electrons will
shift to 3d-orbital making 4s-orbital vacant.
[CoF•]'·: 11~! ! If If If I
 ◄s ~ ◄d The complex ion has inner orbital octahedral
E) ~ jxxj,ocl I geometry (low spin) and is paramagnetic due to
the presence of one unpaired electron.
six electron pairs
donated by F- ions 69. [Fe(H2O)6]'' :
(sp'Jl hybridization) Fe atom (Z = 26)
[Co(C20,l,J'-: 3tJ'> 4.v' ~
3d 4s ~ 4d Ground state : IHI f I f I f I f I lfil LLLJ
11~,1~,1~F ·H 1•3 ~ =1=~I'.'.:I== 3d' 4s ~
'------..------
six electron pairs
Fe"ion : I f If If If If ! I ] L...L.LJ
donated by c10!-ions [Fe(H,O)6 )":
(d2sp3 hybridization) Jd5 4., ~ 4d
I I I I I I §l ~ Hx~ I
1 1 1 1 1
(i) [Co(C20,),)'- is diamagnetic as all electrons
$p3d 2hybridisation
are paired.
six pairs of electrons
(ii) (Co(C,O,>,)'- is more stable as c,oJ- is a from six H2O ligands
(weak ligand)
chelating ligand and forms chelate rings.
(iii) (CoF6)'- is outer orbital complex as it The complex ion has outer orbital octahedral
geometry (high spin) and is paramagnetic due to
undergoes sp'd' hybridization using the outer
the presence of five unpaired electrons.
4d-orbital.
70. (i) For d' ion, if 6.0 < P, the fourth electron
(iv) (Co(C2O,>,)'- is low spin complex due to
enters one of the et orbitals giving the configuration

E
absence of any unpaired electron.
67. (a) Due to the presence of weak field ligand,
l~g e}
Ligands for which 6.0 < P are known as
weak field ligands and form high spin complexes.
i.e., CJ- in the complex [NiCJ,]'- two unpaired
(ii) Refer to answer 63.
electrons are present in 3d-orbitals of Ni-atom
71. (i) Oxidation state of Co ion in (CoF6 )'· is
hence, this complex is paramagnetic in nature.
+3.
On the other hand, due to the presence of strong 3d 4s ◄p ◄d

field ligand i.e., CN- in the complex [Ni(CN),]'-, Co''=lnltltltltlLJ □=DI 11111
(In ground state)
no unpaired electron is present in 3d-orbitals of
[CoF,]'·:
Ni-atom (as strong field ligand causes pairing of
3d' 4s ~ 4d
electrons), hence, it is diamagnetic in nature. In I f I f I f I f I §l ~ )xxH I
(b) In tetrahedral coordination entity formation,
splJ2 hybridisation
the d-orbital splitting is smaller. Consequently, six pairs of electrons
the orbital splitting energies are not sufficiently from six F-ion
(Weak ligands)
large to force pairing and therefore, low spin
configurations are rarely observed. Structure - Outer orbital octahedral complex

68. Fe atom (Z = 26)

F p-
3d6 4, 2 4p
0 F'to,,-F
Ground state : I H I I I I I I I I I fill ITIJ F_,. I '-F
F
3d5 4s 4p
Nature - Paramagnetic
Fe'• ion: 11111111111 □ ITIJ (ii) In [Ni(CN),]'- : Ni is present as Ni(II) with
3d8 configuration.
[Fe(CN)6]'- ion IHI HI f jx~H § I ~ 3J 4s 4p
d2sp3 hybridisation
(strong ligand)
Ni":!HIHIHI f If □ I ITIJ
(In ground state)
[Ni(CN),]'-: IHI HIH IH lxxl B ~ 77. Refer to a11swer 74.
78. Refer to a11swer 71 (ii).
dspl hybridi~tion
four electrons pairs 79. In presence of CN-, the 3d electrons pair
donated by four
CN ions up leaving only one unpaired electron, the
(Strong ligand) hybridisation is d'sp' forming an inner orbital
The complex ion has square planar geometry and octahedral complex whereas in the presence
is diamagnetic in nature. of H,O, 3d electrons do not pair up. The
72. Refer to a11swer 7l(i). hydridisation is sp'd' forming an outer orbital
IUPAC Name: Hexafluoridocobaltate(III) ion octahedral complex containing five unpaired
electrons. Hence, it is strongly paramagnetic.
73. Refer to a11swer 7l(ii).
IUPAC name: Tetracyanidonickelate(II) ion 80. (i) [Co(NH1) 5Cl)Cl2 :Pentaamminechlorido-
74. Oxidation of cobalt in[Co(NH3)6]'• is +3. cobalt (III) chloride.
Co(III) : [Ar]3d"4.s": d'sp' hybridisation leads to
3,/' 4,• 4P°
Co'': IHltltltltl I=:] ITIJ octahedral shape.
Magnetic behaviour : Diamagnetic.
Ground State
Stereochemistry : Complex [Co(NH1) 5Cl)Cl2 do
[Co(NH,J,J" ion: IHI HI Hlxxj.xj B ~ not exhibit geometrical and optical isomerism.
i 1·,,pl hybridisution (ii)K2 (Ni(CN)4 ):Potassiumtetracyanidonickelate(II)
six pairs of electrons Ni(II) : [Ar) 3d"4.s" - dsp' hybridisation leads to
from six NH 3 ligand
(Strong ligand) square planar shape.
Magnetic behaviour : Diamagnetic.
Hybridisation - d'sp' NH
3
l3• Stereochemistry : Complex (Ni(CN),) do not
Structure - Octahedral H3N~·j··_;,:NH 31
: c;;o : exhibit geometrical isomerism and optical
(low spin)
Nature- Diamagnetic H3N/.~•• :\:NH isomerism because all the possible arrangement
NH3 3 are equivalent.
IUPAC name: Hexaamminecobalt(lll) ion 81. (i) [Fe(H,O),]'• :
7S. (i) [Co(en),Cl(NH,))'' Fe atom (Z = 26)
Am mi nech loridobis(ethane-1,2-diamine)cobalt( 111) Jd" 4s' ~
ion Ground state : H I l f I f I f I f I [ill L...LLJ
In presence of strong NH, and e11 ligand, Co'• 3d' 4, ~
(3d") forms low spin complex. Hence, complex is Fe''ion: IHI f If If If 11 J L...LLJ
diamagnetic.
[Fe(HiO),J":
(ii) [Ni(C2O,) 2(H 2O),]'·:
3d' 4, ,........Y.--, 4d
Diaquadioxalatonickelate(II) ion
In the presence of weak HiO and ox ligand, Ni(II) !Hl f l f If l I I Ix~ ~ Ix xix xi l
forms high spin complex (sp3d 2 hybridisation). It sp 3d 2 hybridisation
is paramagnetic. six pairs of electrons
from six H2O ligands
76. (i) In presence of strong field ligand, Co(II) (weak ligand)
has electronic configuration tf,e;.
The complex ion has outer orbital octahedral
geometry (high spin) and is paramagnetic due to
----~~•~ t,,,,>P the presence of four unpaired electrons.
--1,,
(ii) Refer to a11swer 7l(ii).
It can easily lose one electron present in e1 orbital
to give stable 11, configuration. This is why Co2' is 82. Tetrachloridonickelate(II) ion
easily oxidised to Co" in the presence of strong Ni atom (Z = 28) 0
field ligand. 3/ 4s' 4p
(ii) Refer to answers 7l(ii) and 63. l l I I I
Ground state: HI 11 11 t t [ill ~
 3/ 4,° 4p
0 Tetraamminedichloridocobalt (lll) chloride
Ni 2'ion: lnlnlul I I I ID ITO It is octahedral and diamagnetic.
(iii) Ni(CO),: Tetracarbonylnickel(0)
[NiCl,)'-:11111111111 It I§ I ~ It is tetrahedral and diamagnetic.
spJ hybridisation 85. (i) [Fe(CN)6 J'- : Hexacyanidoferrate(Il) ion
four pairs of electrons Hybridisation - d'sp'
from four Cl ligands
(weak ligands) Structure: Inner orbital octahedral complex
4
The complex ion has tetrahedral geometry and
is paramagnetic due to the presence of unpaired cN,._J:,....cNl -
electrons. [ cN,.... I '-cN
83. The difference ofenergy between two splitted CN
Oc1ah<dral
levels of d-orbitals is called crystal field splitting
(ii) [Cr(NH,),Cl2)':
energy. It is denoted by ti. or IO Dq.
For octahedral !J.0, for tetrahedral it is !J., and for Tetraamminedichloridochromium(III) ion
square planar !J.,p· Hybridisation - d2sp3

I Structure : Inner orbital octahedral complex

i•
i E
Degenerate L\or IODq
H3N'- NH
tr:..NH3
d-orbitals '----''---
Splined d-orbitals H 3N/ I '-cl
Cl
(i) When !J.0 > P, r,, ~
Octah<dr.il
(iii) [Ni(CN),)2- : Tetracyanidonickelate(Il) ion
(ii) When !J.0 < P, t1, c~ 2
Hybridisation - dsp
84. (1) [Pt(NH,),Cl(NO2)[ : Structure - Square planar
Diamminechloridonitrito-N-platmum(ll)
It is square planar and diamagnetic. ["Nc,Ni,....crf
(ii) [Co(NH,)4Cl2 )CI: [!.ic,.... '-c~
Square planar

86.
Formulae Name of the Complex Hybridisation Geometry of Magnetic
of metal complex behaviour
ion involved (stereocbemistry)

(i) K,[Mn(CN)6 1 Potassium hexacyanidomanganate(II) d 2sp' Octahedral Paramagnetic

(ii) [Co(NH,),Cl[CI, Pentaamminechloridocobalt(Ill) chlorid, d 2sp' Octahedral Diamagnetic
(iii) K2[Ni(CN),) Potassiumtetracyanidonikelate (JI) dsp2 Square planar Diamagnetic

None of these complexes will show stereoisomerism.

87. (i) [Fe(en) 2Cl2]CI Cl 73+
x+0x2+(-l)x2+(-l)x I =0
r:\·17:\
x= +3 en; Fe.,. ; ep
Oxidation number of iron = + 3 V.j.~
(ii) d2sp' hybridisation and octahedral shape. Cl
(iii) Paramagnetic due to presence of one trans-his(cthanc-1.2-diaminc) ci.J-b;s(cthane-1.2--diaminc)
dichloridoiron(III) chloride dichloridoiron(III) chloride
unpaired electron.
(v) cis-[Fe(en),Cl2 ) has optical isomer.
(iv) 2, cis- and trans-isomers.
 o donor as well as 11 acceptor by back bondi ng.
Hence, M-C O bond is stronger.

M~
(I
CO
NH 3 is electr on pair donor only. Accumulation of
Mirror lae,'O
negative charge on the metal ion takes place, hence
(vi) dichlo ridobi s(etha ne-1,2 -diam ine)ir on(III ) M-N H3 bond is weaker.
chloride M~N H 3
88. 90. Refer to answer 89.
Comp lex Cen- Hybri di- Gtom - Mag-
tral sation of ttryol ndic 91. Because CO has vacant molecular orbitals
metal mttal com- behav- with which it can form it-bon d with metal throu gh
ion/ ion in- plex iour back donation.
atom volvtd 92. (i) Na2EDTA is used for estimation of
(i) !Cr(NH,).ct,JCI er'· d'sp' Octa- Para- hardness of water.
hedral magnttic (ii) Wilkinson's catalyst is used as catalyst for
(ii) !Co(tn )i]Cl, Co'' d'sp' Octa- Diamag-
hydrogenation.
hedral nctic
(iii )K,INi(CN),] Ni2.. dsp' Square Diamag- 93. cis-Platin is used in the treatment of cancer.
planar nelic EDTA is used in lead poisoning.

89. Ln CO both lone pairo felectrons and vacant 11•

orbitals are present. Hence, it acts as electron pair