CHAPTER 5: COORDINATION COMPOUDS

• Coordination compounds have a central atom (or cation) that is coordinated to a number of anions
or neutral molecules, and they usually retain their identity in both solution and solid state.
• These can be positively, negatively, or neutrally charged species, such as [Co(NH3)6]3+, [NiCl4]2-,
[Ni(CO)4], and so on.
• In 1893, Werner proposed a theory to explain coordination compound structure and bonding.
• According to this theory metals have two types of valencies in coordination compounds: primary
valency and secondary valency.
• Primary valencies are ionisable.
• Secondary valencies cannot be ionized.

On the basis of Werner’s theory the structure of [Co(NH3)5Cl]

Cl2 is:

DIFFERENCE BETWEEN DOUBLE SALTS AND COORDINATION COMPOUNDS.

COORDINATION COMPOUNDS DOUBLE SALT

A coordination compound contains a central When two salts in stoichiometric ratio are
metal atom or ion surrounded by number of crystallised together from their saturated
oppositely charged ions or neutral solution they are called double salts
molecules. These ions or molecules are
bonded to the metal atom or ion by a
coordinate bond.

Example: K4 [Fe(CN)6 ] Example: FeSO4 . (NH4)2SO4 .6H2O

(Mohr’s salt)

They do not dissociate into simple ions They dissociate into simple ions when
when dissolved in water. dissolved in water.
Ligands:

• Definition: Ligands are molecules or ions that donate electrons to a metal ion and form coordinate
covalent bonds. Ligands can be classified into various types based on their structure and properties.

• Classification based on denticity: Ligands can be classified as monodentate, bidentate, tridentate,

etc., based on the number of donor atoms they can use to bind to a metal ion.

• Chelating ligands: Chelating ligands are ligands that can bind to a metal ion through more than one
donor atom. Chelating ligands form stable complexes and play an important role in many biological
processes.

• Polydentate ligands: Polydentate ligands are ligands that have multiple donor atoms and can bind to
more than one metal ion. Polydentate ligands play an important role in the formation of coordination
polymers and metal complexes with high stability.

• Coordination sphere & Counter Ions. The central atom/ion and the ligands attached to it are enclosed
in square bracket and is collectively termed as coordination sphere and the ionizable groups written
outside the coordination sphere is called counter ions etc. In K4[Fe(CN6)]
[Fe(CN)6]4− is coordination sphere
K+ is counter ion

Coordination number: The coordination number in coordination compounds is defined as the

number of ligand (donor) atoms/ions surrounding the central metal atom in a complex ion. For
example, the coordination number of cobalt in [Co(NH3)6]3+ is six. Similarly the coordination
number of Ag+ in [Ag(NH3)2]+ is 2, that of Cu2+ in [Cu(NH3)4]2+ is 4, and that of Fe3+ in
[Fe(CN)6]3– is 6.
Coordination polyhedra: the spatial arrangement of the ligand atoms which are directly attached to the

central atom / ion.

 Oxidation number: Another important property of coordination compound is the oxidation number of
the central metal atom. The net charge on a complex ion is the sum of the charges on the central atom
and its surrounding ligands. In the [PtCl6]2- ion for example, each chloride ion has an oxidation
number of–1, so the oxidation number of Pt must be +4. If the ligands do not bear net charges the
oxidation number of the metal is equal to the charge of the complex ion. Thus in [Cu(NH3)4]2+ each
NH3 is neutral, so the oxidation number of copper is +2.

Magnetic properties of coordination compounds: A coordination compound is paramagnetic in

nature, if it has unpaired electrons and diamagnetic if all the electrons in the coordination compound
are paired. Magnetic moment = [n (n + 2)]1/2 where n is number of unpaired electrons.

Rules for naming mononuclear coordination compounds

1. Order of naming ions

The positive ion (cation) whether simple or complex, is named first followed by the negative ion
(anion). The name is started with a small letter and the complex part is written as one word.

2. Naming ligands

3. i) Negative ligands (organic or inorganic) end in −O, eg, CN− (cyano), Cl− (chlorido), Br−
(bromido), F- (fluorido), NO2− (nitro), OH- (hydroxo), O2− (oxo), H- (hydrido).
If the name of the anionic ligands ends in −ide, −ite or −ate, the last ‘e’ is replaced by ‘O’ giving −ido,
−ito and −ato eg, SO42− (sulphato), C2O42− (oxalato), NH2− (amido), NH2− (imido), ONO− (nitrito).

• ii) Neutral ligands have no special ending, NH3 (ammine), H2O (aqua), CO (carbonyl)

• iii) Positive ligands (which are very few) end in -ium, NO+ (nitrosoium), NO2+ (nitronium)

3. Numerical prefixes to indicate number of ligands

If there are several ligands of the same type, the prefixes like di, tri, tetra, penta and hexa are used to
indicate the number of ligands of that type.
When the name of polydentate ligand includes a number e.g., ethylendediamine, then bis, tris, tetrakis
are used as prefixes.

4. Order of naming of ligands

All ligands whether negative, neutral or positive are named first in the alphabetical order followed by
the name of the metal atom/ion.

5. Naming of the complex ion and ending of the central atom

Ligands are named first followed by the metal atom.

a) If the complex ion is a cation or the coordination compund is non-ionic, the name of the central metal ion is
written as such followed by its oxidation state indicated by Roman numeral (such as II, III, IV) in the
parentheses at the end of the name of the metal without any space between the two.
b) If the complex ion is anion, the name of the central metal atom is made to end in-ate followed by the
oxidation number in brackets without any space between them.

Rules for Writing Formula from the Name of the Mononuclear Complex

Formula of the cation (whether simple or complex) is written first followed by that of the anion.

The formula of the complex ion (coordination entity) (whether charged or not) is written in square
brackets called coordination sphere.

Within the coordination sphere, the symbol of the metal atom is written first followed by the
symbols/formulas of the ligands arranged alphabetically according to their names irrespective of the charge
present on them.
While listing the ligands alphabetically, the following rules should be followed:

i) Polydentate ligands are also listed in the alphabetical order.

ii) The position of abbreviated ligands in the alphabetical order is determined from the first letter of
the abbreviation.

iii) The position of ligands with special names (such as aqua for water) in the alphabetical order is
determined from the first letter of the special name.

iv) Abbreviations used for the ligands and the formulas of the polyatomic ligands are enclosed in
parentheses separately.

v) The metal atom as well as all the ligands are listed without any space between them.

If the formula of the complex ion is to be written without writing the counter ion, the charge on the
complex ion is indicated outside the square bracket as a right superscript with the number before the sign. For
example, [Fe(CN)6]3-, [Cu(NH3)4]2+, etc.

The number of cations or anions to be written in the formula is calculated on the basis that total
positive charge must be equal to the total negative charge, as the complex as a whole is electrically neutral.
Example : Tetraammineaquachloridocobalt(III) chloride has complex ion = [Co(NH3)4(H2O)Cl] and simple
ion = Cl-
To balance the charge, the formula will be [Co(NH3)4(H2O)Cl]Cl2
 SECTION A:

MCQ (1 MARKS):

1. The correct name of the compound [Cu(NH3)4](NO3)2 according to IUPAC system is

(a) Cuprammonium nitrate

(b)Tetrammonium copper (II) dinitrate

(c) tetraamminecopper (Il) nitrate

(d) tetrammine copper (II) dinitrite

2. Coordination number and oxidation number of Cr in K2[Cr(C2O4)3] are, respectively?

(a) 4and +2

(b) б апd +3

©З апd +3

(d) З апd 0

3. Which of the following is a negatively charged bidentate ligand?

(a) Dimethylglyximato

(b) Cyano

(c) Ethylenediamine

(d) Acetato

4. The oxidation number of Cobalt in K[Co (CO)4] is

(a) +1

(b) +3

(c) -1

(d) -3

5. Amongst the following ions, which one is highly paramagnetic?

(a) [Cr (H2O)6] 3+

(b) [Fe(H2O)6] 2+
(c) [Cu(H2O)6] 2+

(d) [Zn(H2O)6] 2+

6. The spin only magnetic moment of [Ni(Cl4)]2- is

(a) 1.82 BM (b) 5.46 BM (c) 2.82BM (d) 1.41 BM

7. The IUPAC name of complex ion ,[Fe(CN)6] 3- is

(a) Hexacyanidoiron(III)ion

(b) Hexacyanatoferrate (III)ion

(c) Hexacyanidoferrate (III)ion

(d) Tricyanoiron(III)ion

8. The geometry and magnetic behaviour of the complex [Ni(CO)4] are

(a) Square planar and paramagnetic

(b) Tetrahedral and diamagnetic

(c) Square planar and diamagnetic

(d) Tetrahedral and paramagnetic

9. The hybridisation involved in the complex [Ni(CN)4] 2- is

(a) d 2 sp2

(b) d 2 sp3

(c) dsp2

(d) sp3

10. The geometry of [Ni(CN)4] 2- and [NiCl4] 2- are

(a) Both square planar

(b) Both tetrahedral

(c) Tetrahedral and square planar respectively

(d) Square planar and tetrahedral respectively

11. The diamagnetic species is

(a) [Ni(CN)4] 2-

(b) [NiCl4] 2-

(c) [CuCl4] 2-

(d) [CoF6] 3-

12. Correct increasing order for the wavelengths of absorption in the visible region in the complexes of Co3+
is

(a) [Co(H2O)6] 3+ , [Co (en)3] 3+ , [Co(NH3)6] 3+

(b) [Co(H2O)6] 3+, [Co(NH3)6] 3+ , [Co (en)3] 3+

(c) [Co(NH3)6] 3+, [Co (en)3] 3+, [Co(H2O)6] 3+

(d) [Co (en)3] 3+,[Co(NH3)6] 3+, [Co(H2O)6] 3+

ASSERTION – REASON TYPE QUESTIONS

In the following questions, a statement of Assertion followed by a statement of Reason is given. Choose the
correct option out of the following choices.

(a) Assertion and Reason both are true, Reason is the correct explanation of Assertion .
(b) Assertion and Reason both are true but Reason is not the correct explanation of Assertion
(c) Assertion is true, Reason is false.
(d) Assertion is false, Reason is true.
13. Assertion: The crystal field theory is successful in explaining the formation, structure, colour and
magnetic properties of coordination compounds.

Reason: crystal field theory considers the metal-ligand bond to be ionic.

Ans: (b) Assertion and Reason both are true but Reason is not the correct explanation of Assertion

14. Assertion: Linkage isomerism arises in coordination compounds containing ambidentate ligands

Reason: Ambidentate ligand has two different donor atoms

Ans: (a) Assertion and Reason both are true, Reason is the correct explanation of Assertion.

15. Assertion: CO is stronger ligand than NH3 for many metals

Reason: NH3 can form pi bonds by back bonding

Ans: (c) Assertion is true, Reason is false.

 SECTION B:

(2MARKS)

16. Give reasons

(i)CuSO4 5H2O is blue in colour while CuSO4 is colourless.

Ans. In CuSO4 5H2O , water acts as ligand and causes crystal field splitting. Hence d-d transitionis possible
and shows colour.

(ii)Low spin tetrahedral complexes not formed

Ans:In a tetrahedral complex, the d-orbital is split too small as compared to octahedral complex. For the same
metal and same ligand Δt = 4/9Δ[Link], the orbital energies are not enough to force pairing. As a result, low
spin configurations are rarely observed in tetrahedral complexes.

17. Arrange the following complexes in the increasing order of conductivity of their solution: [Co(NH3)3Cl3],
[Co(NH3)4Cl2]CI, [Co(NH3)6]Cl3, [Cr(NH3)5Cl]Cl2

Ans: Co(NH3)3Cl3] < [Co(NH3)4Cl2]Cl < [Cr(NH3)5Cl]Cl2 < [Co(NH3)6]Cl3 Here, the number of ions
increases and conductivity increases.

18. A coordination compound CrCl3. 4H2O precipitates silver chloride when treated with silver nitrate. The
molar conductance of its solution corresponds to a total of two ions. Write the structural formula of the
compound and name it.

Ans: Silver chloride precipitates when treated with silver nitrate because there is chloride ion outside the
complex. There is only one chloride ion outside the complex since only two ions are generated. As a result,
the compound’s structural formula and nomenclature are: [Co(H2O)4Cl2]Cl – Tetraaquadichloridocobalt(III)
chloride

19. Explain why [Fe(H2O)6] 3+ has a magnetic moment value of 5.92 BM whereas [Fe(CN)6] 3- has a value of
only 1.74 BM.

Ans:[Fe(CN)6] 3– involves d2 sp3 hybridisation with one unpaired electron and [Fe(H2O)6] 3+ involves sp3 d
2 hybridisation with five unpaired electrons. This difference is due to the presence of strong ligand CN– and
weak ligand H2O in these complexes.

20. [Ni(CN)4] 2- is colourless where as [Ni(H2O)6] 2+ is green. Why?

Ans:In [Ni(CN)4] 2- , Ni is in +2 oxidation state with electronic configuration 3d8 . In the presence of strong
CNligand the two unpaired electron in 3d orbital pair up. As there is no unpaired electron, it is colourless. In
[Ni(H2O)6] 2+ Ni is +2 oxidation state and electronic configuration 3d8 . The two unpaired electrons do not
pair up in the presence of weak ligand H2O. The d-d transition absorbs red lightand complementary green
light is emitted.
[Link] the formula of each of the following coordination entities: (i)Co 3+ ion bound to one Cl- , one NH3
molecule and two ethylene diamine molecules. (ii)Ni 2+ ion is bound to two water molecules and two oxalate
ions.

Ans. (i) [Co (NH3)Cl (en)2] 2+ (ii)Ni(H2O)2(ox)2] 2-

22. Explain the following terms giving a suitable example in each case : (i) Ambident ligand (ii) Denticity of a
ligand

Ans: Denticity : The number of coordinating groups present in a ligand is called the denticity of ligand. For
example, bidentate ligand ethane-1, 2-diamine has two donor nitrogen atoms which can link to central metal
atom.

Ambidentate ligand : A unidentate ligand which can coordinate to central metal atom through two dierent
atoms is called ambidentate ligand. For example NO2 – ion can coordinate either through nitrogen or through
oxygen to the central metal atom/ion.

23. Using IUPAC norms write the formulae for the following coordination compounds : (i)
Hexaamminecobalt(III)chloride (ii) Potassiumtetrachloridonickelate(II)

Ans: (i) [Co(NH3)6]Cl3 (ii) K2[NiCl4]

24. Write the name and draw the structures of each of the following complex compounds: (i)
[Co(NH3)4(H2O)2]Cl3 (ii) [Pt(NH3)4][NiCl4]

25. For the complex [Fe(H2O)6] 3+, write the hybridization magnetic character and spin of the complex. (At
number Fe = 26)

Ans:

The complex ion has outer orbital octahedral geometry (high spin) and
is paramagnetic due to the presence of five unpaired electrons.
 SECTION C:

(3MARKS)

26. .[Ni(CO)4] possesses tetrahedral geometry while [Ni(CN)4] 2- is square planar. Why?

Ans. In [Ni(CO)4] Ni is in 0 oxidation state and its electronic configuration is 3d8 4s2 . CO is strong ligand.
Hybridization is sp3 and it is tetrahedral.

27. For the complex [Fe(en)2Cl2], Cl, (en = ethylene diamine), identify (i) the oxidation number of iron, (ii)
the hybrid orbitals and the shape of the complex, (iii) the magnetic behaviour of the complex,

Ans: (i) [Fe(en)2Cl2]Cl x + 0 × 2 + (–1) × 2 + (–1) × 1 = 0 \ x = 3 Oxidation number of iron = 3

(ii) d2 sp3 hybridisation and octahedral shape.

(iii) Paramagnetic due to presence of one unpaired electron.

28. Compare the following complexes with respect to their shape, magnetic behaviour and the hybrid orbitals
involved : (i) [CoF4] 2- (ii) [Cr(H2O)2(C2O4)2]– (iii) [Ni(CO)4] (Atomic number : Co = 27, Cr = 24, Ni =
28)

29. Write the IUPAC name, deduce the geometry and magnetic behaviour of the complex K4[Mn(CN)6].
[Atomic no. of Mn = 25]
30. Write the state of hybridization, the shape and the magnetic behaviour of the following complex entities :
(i) [Cr(NH3)4Cl2]Cl (ii) [Co(en)3]Cl3 (iii) K2[Ni(CN)4]

31. How is the stability of a co-ordination compound in solution decided? How is the dissociation constant of
a complex defined?

Ans: The stability of a complex in solution refers to the degree of association between the two species
involved in the state of equilibrium. -e magnitude of the equilibrium constant for the association,
quantitatively expresses the stability. -e instability constant or dissociation constant of coordination compound
is dened as the reciprocal of the formation constant.

32. Explain the following : (i) Low spin octahedral complexes of nickel are not known. (ii) -e p-complexes are
known for transition elements only. (iii) CO is a stronger ligand than NH3 for many metals.

Ans: (i) Nickel forms octahedral complexes mainly in +2 oxidation state which has 3d8 configuration. In
presence of strong field ligand also it has two unpaired electrons in eg orbital.

Hence, it does not form low spin octahedral complexes.

(ii) the transition metals/ions have empty d orbitals into which the electron pairs can be donated by ligands
containing p electrons. For example: CH2= CH2 and C6H6, C5H5 – .
(iii) Co is stronger ligand than NH3 because CO has vacant molecular orbitals with which it can form p-bond
with metal through back donation.

33. (i) Write down the IUPAC name of the following complex. [Cr (en)3]Cl3 (ii) Write the formula for the
following complex. Potassium trioxalato chromate (III)

Ans: Tris(ethylenediammine)chromium(III) chloride (ii) K3[Cr(ox)3]

34. Write the hybridization and shape of the following complexes: (i) [CoF6] 3– (ii) [Ni(CN)4] 2

35. For the complex [NiCl4] 2–, write (i) the IUPAC name (ii) the hybridization type (iii) the shape of the
complex. (Atomic no. of Ni = 28)

(i) Tetrachloridonickelate(II) ion

 SECTION D:

(4MARKS)

CASE BASED QUESTIONS:

36. Read the given passage and answer the questions that follow:

Complex compounds play an important role in our daily life. Werner’s theory of complex compounds says
every metal atom or ion has primary valency (oxidation state) which is satisfied by –vely charged ions,
ionisable where secondary valency (coordination number) is nonionisable, satisfied by ligands (+ve, –ve,
neutral) but having lone pair. Primary valency is nondirectional, secondary valency is directional. Complex
compounds are name according to IUPAC system. Valence bond theory helps in determining shapes of
complexes based on hybridisation, magnetic properties, outer or inner orbital complex. Complex show
ionisation, linkage, solvate and coordination isomerism also called structural isomerism. Some of them also
show stereoisomerism i.e. geometrical and optical isomerism. Ambidentate ligand are essential to show
linkage isomerism. Polydentate ligands form more stable complexes then unidentate ligands. There are called
chelating agents. EDTA is used to treat lead poisoning, cis-platin as anticancer agents. Vitamin B12 is
complex of cobalt. Haemoglobin, oxygen carrier is complex of Fe2+ and chlorophyll essential for
photosynthesis is complex of Mg2+.

(a) What is the oxidation state of Ni in [Ni(CO)4]?

Ans. Zero

(b) One mole of CrCl3 . 6H2O reacts with excess of AgNO3 to yield 2 mole of AgCl. Write formula of
complex. Write IUPAC name also.

Ans. [Cr(H2O)5Cl]Cl2 . H2O, pentaaquachloridochromium (III) chloride.

(c) Out Cis – [Pt(en)2 Cl2] 2+ and trans [Pt(en)2Cl2] 2+ which one shows optical isomerism?

Ans. Cis – [Pt(en)2 Cl2] 2+ shows optical isomerism.

(d) Name the hexadentate ligand used for treatment of lead poisoning.

Ans. EDTA4– (ethylenediamine tetraacetate)

(e) What is hybridisation of [CoF6] 3–? [Co = 27] Give its shape and magnetic properties.

Ans. Sp3 d 2 , octahedral, paramagnetic. (f) What type of isomerism is shown by [Cr(H2O)6] Cl3 and
[Cr(H2O)5 Cl] Cl2 .H2O?

Ans. Solvate isomerism.

37. Observe the diagram of splitting of d-orbitals in octahedral field and answer the questions based on the
diagrams and related studied concepts.

(a) What is crystal field splitting anergy?

Ans. The energy difference between the two sets of d-orbitals is called crystal field splitting energy
denoted by ∆0.

(b) Arrange the following complex ions in the increasing order of Crystal field splitting energy [CrCl6] 3- ,
[CrCN6] 3-, [Cr(NH3)6 ] 3+

(c) Ans. [CrCl6] 3- , [Cr(NH3)6 ] 3+ , [CrCl6] 3-

(d) What is relationship between ∆0 (CFSE) and strength of ligand?

Ans. Greater the ∆0(CFSE), more will be strength of ligand

(e) What is electronic configuration of d5 ion if ∆ 0< P?

Ans. t2g 3 eg 2

38. Read the following paragraph and answer the questions.

In 1823, Werner put forth this theory to describe the structure and formation of complex compounds or
coordination compounds. It is because of this theory that he got the Nobel prize and is known as the father
of coordination chemistry. According to his theory The central metals of coordination compounds exhibit
two types of valencies, primary valency and secondary valency. The primary valencies are ionizable.
These are written outside the coordination sphere. These are nondirectional and do not give any geometry
to complex compound. The secondary valency of metals is either by negative ions or neutral molecules or
both. In modern terminology it represents the coordination number of the metal. Secondary valencies are
written inside the coordination sphere. These are directional in nature and give definite geometry to the
complex. These are non-ionisable.

(a)A coordination compound CrCl3.4H2O precipitates silver chloride when treated with silver nitrate. The
molar conductance of its solution corresponds to a total of 2 ions. Write the structural formula of the
complex.

Ans. [Co(H2O)4Cl2]Cl

(b)The increasing order of conductivity of the following complexes in their solutions [Co(NH3)3Cl3] ,
[Co(NH3)6]Cl3 ,[Co (NH3)4Cl2]Cl

Ans. [Co(NH3)3Cl3], ,[Co (NH3)4Cl2]Cl, [Co(NH3)6Cl3

(c)Write the correct formula for the following coordination compound CrCl3.6H2O with 3 chloride ions
precipitated as AgCl.

Ans.[Cr(H2O)6]Cl3

(f) How many ions are produced from the complex [Co(NH3)5Cl]Cl2 in solution ? Ans.3

39. Read the following paragraph and answer the questions.

Valence bond theory considers the bonding between metal and the ligands as purely covalent. On the
other hand the crystal field theory considers the bond to be ionic purely arising from electrostatic
interactions between the metal ion and the ligands. In coordination compounds the interaction between the
metal ion and the ligands causes the 5 d orbitals to split up. This is called crystal field splitting and the
energy difference between the two sets of orbitals is called crystal field splitting energy. CFSE depends
upon the nature of the ligand.

(a)Write the electronic configuration of [CoF6] 3- on the basis of crystal field theory Ans. Co3+ has ( d 6 )
; t2g 4 eg 2 configuration

(b)Arrange the following complex ions in the increasing order of crystal field splitting energy [CrCl6] 3- ,
[Cr(CN)6] 3- ,[Cr(NH3)6] 3+ Ans. [CrCl6] 3- , [Cr(NH3)6] 3+,[Cr(CN)6] 3

(dCAmong the ligands ,NH3 ,en and CO which ligand is having the highest field strength ?

[Link]

(d)What will be the increasing order for the wave lengths of absorption in the visible region of the
following : [Ni (NO2)6] 4- , [Ni (NH3)6] 2+,[Ni (H2O)6] 2+

Ans. [Ni (H2O)6] 2+, [Ni (NH3)6] 2+, [Ni (NO2)6] 4-

 SECTION E

(5 MARKS)

40. (a) Give two examples of coordination compounds used in industries.

(b) Using valence bond theory, explain the geometry and magnetic behavior of [Co(NH3)6]3+
(At. no. of Co = 27)

Ans: (a) Examples:

(i) Pure Ni can be obtained from Ni(CO)4
(ii) Gold and Ag are extracted by the use of complex formation like Na[Ag(CN)2].

41. (a) How is a double salt different from a complex?

(b) Write IUPAC names of the following:
(i) K3[Fe(C2O4)3]
(ii) [Pt(NH3)6]Cl4.
(c) Draw the structure of cis isomer of [CO(NH3)4Cl2]+

Ans: (a) Double salt dissociates completely into its constituent ions in their aqueous solution.
Example : KCl.MgCl2.6H2O dissociates into K+, Cl–, Mg2+ and H2O
Complex does not dissociate into its constituent ions.
Example : K4[Fe(CN)6] → 4K+ + Fe(CN)6]4-

(b) (i) K3[Fe(C2O4)3] IUPAC name : Potassium trioxalatoferrate (III)

(ii) [Pt(NH3)6]Cl4 IUPAC name : Hexaammine Platinum (IV) chloride

(c) Structure of cis isomer of [CO(NH3)4Cl2]+

42. When a coordination compound CrCl3.6H2O is mixed with AgNO3 solution, 3 moles of AgCl are
precipitated per mole of the compound. Write :
(i) Structural formula of the complex
(ii) IUPAC name of the complex
(iii) Magnetic and spin behaviour of the complex

Inner orbital complex so it is low spin complex.

Since 3 unpaired electrons are present, it is paramagnetic in nature.

43. (i) What type of isomerism is shown by the complex [Co(NH3)6][Cr(CN)6]?

(ii) Why a solution of [Ni(H2O)6]2+ is green while a solution of [Ni(CN)4]2- is colourless? (At. no. of Ni =
28)
(iii) Write the IUPAC name of the following complex: [CO(NH3)5(CO3)]Cl.

Ans: (i) Coordination isomerism

(ii) [Ni(H2O)6]2+ is an outer orbital complex due to weak field ligand H2O and the presence of unpaired
electrons undergoes d—d transition by absorbing red light and shows green colour while [Ni(CN)4]2- is an
inner orbital complex and has no unpaired electrons hence colourless.
(iii) Pentaamminecarbonatocobalt (III)
Chloride***********************************************************************
 COORDINATION COMPOUNDS (2ND HALF)
Section A

● Section A - 1 Mark's MCQ (15)

● Section B - 2 Mark's questions (10)
● Section C - 3 Mark's questions (10)
● Section D - 4 Mark's case study based questions (4 )
● Section E - 5 Mark's questions (4)

MCQ carrying 1 mark each

Q.1. The crystal field splitting energy for octahedral (∆o) and tetrahedral (∆t) complexes is related as -

a) ∆t = 2/9∆o b) ∆ t = 5\9∆o c) ∆t = 4/9∆o d) ∆ t = 2∆o

Q.2. What are the number of unpaired electrons in the square planer [Pt(CN)4]2- ion?

a) 0 b) 1 c) 4 d)6

Q.3. Magnetic nature and spin of [Co(NH3)6]3+ is -

a) Paramagnetic, High spin complex b) Diamagnetic, low spin complex

c) Paramagnetic, low spin complex d) Diamagnetic, high spin complex

Q.4. What was the term proposed by Werner for the number of groups bound directly to the metal ion in a
coordination complex?

a) Primary valence

b) Secondary valence

c) Oxidation number

d) Polyhedra

Q.5. Werner postulated that octahedral, tetrahedral and square planar geometrical shapes are more common in
coordination compounds of ________

a) alkali metals

b) lanthanides

c) actinides

d) transition metals

Q.6. What is the sum of the oxidation number of cobalt in [Co(H2O)(CN)(en)2]2+and [CoBr2(en)2]+?
a) +3

b) +4

c) +5

d) +6

Q.7. Hybridisation of [Ni(CN)4]2- is

(a) dsp2

(b) d2sp2

(c) sp3

(d) d2sp3

Q.8. Which of the following is true for the formation of stable bonds according to valence bond theory?

(a) Greater overlapping between atomic orbitals

(b) Close proximity between two atoms

(c) Pairing of electrons having opposite spins

(d) All of the above

Q.9. A coordination complex’s core atom/ion is also known as ________

a) Bronsted-Lowry acid

b) Lewis base

c) Lewis acid

d) Bronsted-Lowry base

Q.10. Which of the following d orbitals take part in the octahedral complex with d2sp3 hybridisation?

(a) dxy, dyz

(b) dxz, dx2−y2

(c) dx2−y2, dz2

(d) dz2, dxz

Q.11. The correct increasing order of splitting power of ligands according to spectrochemical series is

(a) Cl– < OH– < CN–

(b) Cl– < CN– < OH–

(c) OH– < Cl– < CN–

(d) OH– < CN– < Cl–

Q.12. Which of the following is paramagnetic?

(a) [CoBr]42-

(b) Mo(Co)6

(c) [Pt(en)Cl2]

(d) [Co(NH3)6]3+

Q.13. Hardness of water is estimated by simple titration with which compound?

a) Na2(EDTA)

b) Fe(EDTA)

c) Mg(EDTA)

d) Co(EDTA)

Q.14. Haemoglobin is a complex compound of which metal ion?

a) Fe3+

b) Fe2+

c) Co2+

d) Co3+

Q.15. The complex ion [Ag(S2O3)2]3- is associated with which field?

a) Electroplating

b) Medicine

c) Water treatment

d) Photography

Section - B

Q.16. Write the hybridization and shape of the following complexes -

i) [CoF6]3- ii) [Ni(CN)4]2-

Q.17. Why crystal field splitting energy more in case of octahedral complexes as compared to tetrahedral
complexes?
Q.18. Explain crystal field splitting in an octahedral complex.

Q.19. Explain the term spectrochemical series.

Q.20. Using valence bond approach, explain the magnatic character of [Co(NH3)6]3+ ion. (At. No. Of Co =
27)

Q.21. Write the hybridization and shape of the complex [NiCl4 ]2-.

Q.22. Differentiate between weak field and strong field ligand.

Q.23. Why are low spin tetrahedral complexes not formed?

Q.24. Why are different colours observed in Octahedral and tetrahedral complexes for the same metal and
same ligands?

Q.25. CuSO4.5H2O is blue in colour while CuSO4 is colourless. Why?

Section - C

Q.26. Using valence bond theory, explain the following in relation to the complexes given below:

[Mn(CN)6]3-, [Co(NH3)6]3+, [Cr(H2O)6]3+

(i) Type of hybridisation.

(ii) Inner or outer orbital complex.

(iii) Magnetic behaviour.

Q.27. NH3 acts as complexing agent but NH4+ does not, explain.

Q.28. Fe(H2O)6]3− is strongly paramagnetic whereas [Ni(NH3)6]2+

weakly paramagnetic. Explain.

Q.29. Name the central metal atom/ion present in -Chlorophyll, Haemoglobin, Vitamin B-12.

[Link] the limitations of Valence Bond Theory.

Q.31. (i) Low spin octahedral complexes of nickel are not known.

(ii) The π-complexes are known for transition elements only.

Q.32. What is meant by crystal field splitting energy? On the basis of crystal field theory, write the electronic
configuration of d4 in terms of t2g and eg in an octahedral field when

(i) Δ0 > P

(ii) Δ0 < P

Q.33. Discuss the nature of bonding in metal carbonyl.

Q.34. State and describe the factors which govern stability of complexes.

Q.35. Discuss briefly giving an example in each case the role of coordination compound in

(1) biological systems (2) medicinal chemistry (3) analytical chemistry

Section - D

Q.36. Read the passage given below and answer the following questions:

To explain bonding in coordination compounds various theories were proposed. One of the important theory
was valence bond theory. According to that, the central metal ion in the complex makes available a number of
empty orbitals for the formation ofcoordination bonds with suitable ligands. The appropriate atomic orbitals of
the metal hybridise to give a set of equivalent orbitals of definite geometry. The d-orbitals involved in the
hybridisation may be either inner d-orbitals i.e., (n - 1) d or outer d-orbitals i.e., nd. For example, CO3+ forms
both inner orbital and outer orbital complexes, with ammonia it forms [Co(NH3)6]3+ and with fluorine it
forms [CoF6]3- complex ion.

The following questions are multiple choice questions. Choose the most appropriate answer:

(i) Which of the following is not true for [CoF6]3- ?

(a) It is paramagnetic. (b) It has coordination number of 6.

(c) It is outer orbital complex . (d) It involves d2sp3 hybridisation.

(ii) Which of the following is true for [Co(NH3)6]3+ ?

(a) It is an octahedral, dimagnetic and outer orbital complex.

(b) It is an octahedral, paramagnetic and outer orbital complex.

(c) It is an octahedral, paramagnetic and inner orbital complex.

(d) It is an octahedral, dimagnetic and inner orbital complex.

(iii) The paramagnetism of [CoF6]3- is due to

(a) 3 electrons (b) 4 electrons (c) 2 electrons (d) 2 electrons

(iv) Which of the following is an inner orbital or low spin complex?

(a) [Ni(H2O)6]3+

(b)[FeF6]3−

(c) [Co(CN)6]3−

(d) [NiCl4]2−

Q.37. Valence bond theory considers the bonding between the metal ion and the ligands as purely covalent.
On the other hand, crystal field theory considers the metal-ligand bond to be ionic arising from electrostatic
interaction between the metal ion and the ligands. In coordination compounds, the interaction between the
ligand and the metal ion causes the five d-orbitals to split-up. This is called crystal field splitting and the
energy difference between the two sets of energy level is called crystal field splitting energy. The crystal field
splitting energy (Δo) depends upon the nature of the ligand. The actual configuration of complexes is divided
by the relative values of Δo and P (pairing energy)

If Δo < P, then complex will be high spin.

If Δo > P, then complex will be low spin.

The following questions are multiple choice questions. Choose the most appropriate answer :

(i) Which of the following ligand has lowest Δo value?

(a) CN- (b) CO (c) F- (d) NH3

(ii) The crystal field splitting energy for octahedral (Δo) and tetrahedral (Δt) complex is related as

(a) Δt=1/2Δo

(b) Δt=4/9Δo

(c) Δt=3/5Δo

(d) Δt=2/5Δo

(iii) On the basis of crystal field theory, the electronic configuration of d4 in two situations: (i) Δo > P and (ii)
Δo< P are

(iv) Using crystal field theory, calculate magnetic moment of central metal ion of [FeF6]4-.

(a) 1.79 B.M. (b) 2.83 B.M. (c) 3.85 B.M. (d) 4.9 B.M.

Q.38. balance bond theory describe the bonding in complexes in terms of co-ordinate covalent bonds resulting
from overlap filled ligand orbitals with vacant metal hybrid orbitals. The theory explain magnetic behaviour
and geometrical shape of coordination compounds. Magnetic moment of a complex can be determined
experimentally and theoretically by using spin only formula.

Magnetic momentum √n(n+2)BM (n is no. Of unpaired electrons)

(i) write the state of hybridization, shape and the magnetic behaviour of the [Cr(H2O)2(C2O4)2 ]-.

(ii) Why s orbital does not show preference to any direction.

(III) why is [CoF6]3- is paramagnetic but [Co(NH3)6]3+ is diamagnetic in nature?

(IV) Describe the type of hybridization, shape and magnetic property of [Co(NH3)4Cl2]Cl.

Q.39. coordination compound plays many important role in animals and plants they are essential in the storage
and transport of oxygen, as electron transfer agents as catalysts and in photosynthesis. White range of
application in daily life takes place through formation of complexes photo photographic fixing qualitative and
quantitative analysis purification of water, metallurgical extraction are some specific worth mentioning.

(I) Exalic acid is commonly used

(A)To make medicines

(B) To remove rust and stains

(C)as a thinner or in polishing the wooden material

(D)all of the above

(Ii) Ziegler- NATA catalyst is used to convert

(A) ethylene

(b) ethyne

(c) ethanal

(d)ethanol

(III) calcium dihydrogen salt of EDTA is used as an antidote for lead poisoning because

(A) excess EDTA remove Ca2+ ions from body

(b) calcium ions co-ordinates with Lead in the body

(c) excess EDTA will not remove Ca2+ ions from body

(d) b and C

(IV) cis - platin, stands for

(A) cis - diamminechloroplatinum (II)

(b) cis - dichloridodiammineplatinum(I)

(c) cis - dimethyldichloridoplantinum (II)

(d)bcis - dichloridodiammineplatinum (II)

 Section - E

Q.40. Using valence bond theory, explain the following in relation to the complexes given below:

[Mn(CN)6]3-, [Co(NH3)6]3+, [FeCl6]4-

(i) Type of hybridisation.

(ii) Inner or outer orbital complex.

(iii) Magnetic behaviour.

(iv) Spin only magnetic moment value.

Q.41. Explain Werner's theory of coordinate compounds with suitable examples?

Q.42. What is crystal field splitting? Explain crystal field splitting in tetrahedral complexes.

Q.43. a) Explain why [Fe(HO)6]3+ has a magnetic moment value of 5.92 BM whereas [Fe(CN)6]3- has a
value of only 1.74 BM.

b) Why do compounds having similar geometry have different magnetic moments?

MCQ answer key

Q.1. c)

Q.2. a)

Q.3. b)

Q.4. b)

Q.5. d)

Q.6. d)

Q.7. a)

Q.8. d)

Q.9. c)

Q.10. c)

Q.11. a)

Q.12. a)

Q.13. a)
Q.14. b)

Q.15. d)

Section - B Answer key

Q.16. i) In [CoF6]3- cobalt is in+3 O.S.. F- is a weak field ligand. It does not cause pairing.

Therefore cobalt undergoes sp3d2 hybridization and have octahedral geometry.

ii) In [Ni(CN)4]2- Ni is in+2 O. S. and has the electronic configuration 3d84s0. As CN- is strong field ligand
it causes pairing of electrons resulting one 3d orbital empty, with one 4s and two 4p it gives dsp2
hybridization. And shape is square planer.

Q.17. Crystal field splitting energy in Octahedral complexes is more than in tetrahedral complexes, because -

i) in Octahedral complexes there are 6 ligand which face repulsion from valence electrons of central metal
atom. But only 4 ligand in tetrahedral complexes.

ii) Also because in Octahedral complexes 2 ligands approach Central metal atom along the direction of 2 d
orbitals (dx2-y2, dz2). But in tetrahedral complexes all ligands approach the central metal atom between the
axes not along any axes with d orbitals.

Q.18. Crystal field splitting in Octahedral field -In free transition metal ion all d orbitals are equal in energy
called degenerate orbitals. But as soon as ligand approaches the central metal ion, repulsion between electron's
of central metal ion and electron's of ligand causes splitting of 5 degenerate d orbitals into two sets of orbitals.
eg orbitals with 2 orbitals are high in energy and t2g with 3 orbitals low in energy as follows

Q.19. Spectrochemical series - The arrangement of ligands in the order of increasing field strength or
increasing crystal field splitting energy values is known as spectrochemical series.

Br-, Cl-,SCN-,F-, OH-, H2O, NH3, en, CN- , CO

Q.20. In [Co(NH3)6]3+ ion O.S. of Co is +3

hybridization in presence of NH3 is strong field ligand

Q.22. Weak field ligand - the ligand which have small value of crystal field splitting energy (∆o). For these
ligands ∆o<P, (p is pairing energy). These ligands produce high spin complexes.

Strong field ligand - the ligand which have large value of crystal field splitting energy and also, ∆o>P. These
ligands produce low spin complexes.

Q.23. For tetrahedral complexes, the crystal field splitting energy is smaller than pairing energy, so pairing
doesn't take place and high spin complexes are formed instead of low spin.

Q.24. ∆t=(4/9)∆o

So, a higher wavelength of light is absorbed in octahedral complexes than tetrahedral complexes for same
metal and ligands. Thus, different colours are observed.

Q.25. Water acts as a ligand in CuSO4.5H2O, causing crystal field splitting. As a result, in CuSO4.5H2O, a
d—d transition is possible and coloured. Crystal field splitting is impossible in anhydrous CuSO4 due to the
lack of water (ligand), hence there is no colour.

Section - C

Q.26. [Mn(CN)6]3-

(i) Type of hybridisation = d2sp3 hybridisation

(ii) Inner or outer orbital complex = Inner orbital complex because (n-1)d – orbitals are used.

(iii) Magnetic behaviour = Paramagnetic, as two unpaired electrons are present.

[Co(NH3)6]3+

(i) Type of hybridisation = d2sp3 hybridisation

(ii) Inner or outer orbital complex = Inner orbital complex (as(n-1)d-orbitals take part.)

(iii) Magnetic behaviour = Diamagnetic (as three paired electrons are present.)

[Cr(H2O)6]3+
(i) Type of hybridisation = d2sp3 hybridisation

(ii) Inner or outer orbital complex = Inner orbital complex as(n-1)d-orbitals take part.)

(iii) Magnetic behaviour = Paramagnetic (as three unpaired electrons are present.)

Q.27. Because ammonia only has one lone pair of electrons, it can accept electrons from coordination
complexes. Ammonia is transformed into an ion called ammonium, which lacks a lone pair to donate and
form complexes. As a result, whereas ammonia can be an excellent ligand, the ammonium ion does not form
complexes.

Q.28. The ligand NH3 is neither a strong field ligand nor a weak field ligand in the [Ni(NH3)6]2+ complex
ion. It is, in fact, a weak strong field ligand. However, because the crystal field stabilisation energy is smaller
than the pairing energy, the ligand NH3 acts as a weak field ligand in the [Ni(NH3)6]2+ ion. As a result, the
electronic configuration under the effect of an octahedral crystal field is t2 g6eg2. The complex has two
unpaired electrons, according to the aforementioned electrical structure. As a result, the [Ni(NH3)6]2+
complex is weakly paramagnetic.

In the complex [Fe(H2O)6]3+ the oxidation state of Fe is +3, having the structure 3 d5. Water (H2O) is a
weak ligand, and 3 d electrons do not couple up in its presence. The sp3d2 hybridization results in an outer
orbital octahedral complex with 5 unpaired electrons. As a result, it is very paramagnetic.

Q.29. The central metal ion in the structure of chlorophyll is magnesium.

The central metal ion in the structure of haemoglobin is iron.

The central metal ion in the structure of vitamin B-12 is cobalt.

Q.30. The limitations of valence bond theory are:

(i) VBT fails in explaining the tetravalency of carbon.

(ii) The geometries of ammonia, water, methane, etc cannot be properly explained by this theory.

(iii) Bond angles of molecules such as carbon dioxide, water, ammonia, etc could not properly be given by
VBT.

(iv) VBT does not explain the magnetic properties of complex

Q.31. (i) The electronic configuration of Ni is [Ar] 3d8 4s2 which shows that it can only form two types of
complexes i.e. square planar (dsp2) in presence of strong ligand and tetrahedral (sp3) in presence of weak
ligand. There are four empty orbitals in Ni while octahedral complexes require six empty orbitals.

(ii) Due to presence of empty d-orbitals in transition metals, they can accept electron pairs from ligands
containing π electrons and hence can form ic-bonding complexes.

Q.32. d-orbital is degenerate which split into two levels eg and t2g in the presence of ligands. This splitting is
due to the presence of ligands. This is called the crystal-field splitting and the energy difference between the
two levels (eg and t2g) is called the crystal-field splitting energy, Δ0 Electrons are singly filled in the t2g
energy levels first and the remaining electrons are filled based on the crystal field splitting energy and pairing
energy.

Filling up of the remainig electrons takes place in two ways.

(i) If the CFSE (Δ0) is greater than that of the pairing energy (p), electrons will be filled in the 'eg' orbitals.

(ii) If the CFSE (Δ0) is lesser than that of the pairing energy (p), electrons will be paired up in the t2g energy
levels.

Q.33. The metal carbon bond in metal carbonyl have both sigma and pi character. The metal carbon sigma
bond is formed by the donation of lone pair of electrons of the carbonyl carbon to a vacant orbital of the
metal. The metal carbon pi bond is formed by the donation of a pair of electrons from a filled d orbital of
metal into the vacant antibonding pi molecular orbitals of carbon monoxide. The metal to ligand bonding
creates a synergic effect which strengthen the bond between CO and the metal.

Q.34. I) Charge on the central metal ion - greater the charge, greater is the stability of complex.
II) Nature of the metal ion- group 3-6 form more stable complexes.

III) Basic nature of the ligands.

IV) presence of chelate rings increases the stability of complex.

V) Multidentate cyclic ligands without any steric effect increases the stability of complex further.

Q.35. Biological systems -

(A) hemoglobin the oxygen carrier in blood is a complex of Fe2+ with porphyrin.

(B) the pigment chlorophyll in plants responsible for photosynthesis is a complex of Mg2+ with porphyrin.

(C) vitamin B12 is a complex of Cobalt.

Medicinal chemistry

(A) the platinum complex cis platin is used in the treatment of cancer.

(B) the excess of copper and iron present in animal system are removed by the chelating ligands.

Analytical chemistry

(A) detection of Cu2+ is based on the formation of a blue Tetra Ammine copper (II) ion.

(B) Ni2+ is detected by the formation of red complex with dimethyl glyoxime.

Q.36. (i) d (ii) d (III) b (iv) c

Q.37. (i) c (ii) b (III) a (iv) d

Q.38.
(ii) The s orbital is spherically symmetric in shape so it does not show preference to any direction. It is the
same from all the directions

(III) In [CoF6]3- unpaired electrons are present in sp3d2 configuration but in [Co(NH3)6]3+ all electrons are
paired in d2sp3 configuration.

(IV) Hybridisation - d2sp3

Shape - Octahedral

Magnetic nature - Diamagnetic

Q.39. (I) b (ii) a (III) c (iv) d

Q.40.

Q.41. 1) Several metals have two types of valence:

i) Primary valence or principal valence or ionisable valence. It is designated by solid line. It corresponds to
oxidation number of the metal ion.

ii) Secondary valence or auxiliary valence or subsidiary valence or residual valence or non ionisable valence.
It is designated by dotted line. It correspond to coordination number.

2) Every metal has tendency to satisfy both valences.

3) Every metal has fixed number of secondary valence

4) The primary valences are non-rigid and non-directional. The secondary valences are directional in nature.
The secondary valence is always directed towards fixed position in space.

5) There are two spheres around the central metal ion. The inner sphere is the coordination sphere and the
outer sphere is the ionization sphere.

6) Groups present in inner sphere are firmly attached to the metal ion and cannot be easily separated. The
groups present in the ionization sphere are loosely bound and can be separated as ions on dissolving the
complex in suitable solvent.

For example, in the complex PtCl4, the primary as well as secondary valencies of Pt metal are 4 each.

Q.42. Crystal field splitting - splitting of 5 degenerate d-orbitals into different set of orbitals in presence of
ligands because of repulsion between the electrons of ligands and valence electrons of central metal atom.

Crystal field splitting in tetrahedral complexes -

Q.43. a) [Fe(CN)6]3– involves d2sp3 hybridisation with one unpaired electron and [Fe(H2O)6]3+ involves
sp3d2 hybridisation with five unpaired electrons. This difference is due to the presence of strong ligand CN–
and weak ligand H2O in these complexes.

b) The presence of weak and strong field ligands in complexes is the reason for this. For example, [CoF6]3-
and [Co(NH3)6]3+ are paramagnetic and diamagnetic respectively, because F is a weak field ligand and NH3
is a strong field ligand while both have similar geometry. Because F is a weak field ligand and NH3 is a
strong field ligand, the complex will have a low magnetic moment if CFSE is high, and vice versa.