COORDINATION COMPOUNDS

Multiple Choice Questions

1. The sum of primary valance and secondary valance of the metal M in the
complex [ M ( en)2 ( Ox)] Cl is L

a) 3

b) 6

c) -3

d) 9

Solution

In the complex [M (en)2 (Ox)] Cl For the central metal ion M3+

The primary valance is = +3

The secondary valance = 6

sum of primary valance and secondary valance = 3+6 = 9

Answer : option (d)

2. An excess of silver nitrate is added to 100ml of a 0.01M solution of pentaaqua

chloride chromium(III)chloride. The number of moles of AgCl precipitated would
be

a) 0.02

b) 0.002

c) 0.01

d) 0.2

Solution
The complex is [M(H2O)5 Cl] Cl2

1000 ml of 1M solution of the complex gives 2 moles of Cl − ions

1000 ml of 0.01M solution of the complex will give

[100 ml x 0.01M x 2Cl-] / [1000 ml x 1M] = 0.002 moles of C− ions

Answer : option (b)

3. A complex has a molecular formula MSO 4 Cl. 6H2O .The aqueous solution of it
gives white precipitate with Barium chloride solution and no precipitate is obtained
when it is treated with silver nitrate solution. If the secondary valence of the metal
is six, which one of the following correctly represents the complex?

a) [M ( H2O)4 Cl] SO4 .2H2O

b) [M ( H2O)6 ]SO4

c) [M ( H2O)5 Cl] SO4 .H2O

d) [M ( H2O)3 Cl ] SO4 .3H2O

Solution

Molecular formula: MSO4Cl. 6H2O .

Formation of white precipitate with Barium chloride indicates that SO 42- ions are
outside the coordination sphere, and no precipitate with AgNO 3 solution indicates
that the Cl− ions are inside the coordination sphere.Since the coordination number
of M is 6, Cl− and 5 H2O are ligands, remaining 1 H2O molecular and SO42- are in
the outer coordination sphere.

Answer : option (c)

4. Oxidation state of Iron and the charge on the ligand NO in [ Fe ( H2O)5 NO]
SO4 are

a) +2 and 0 respectively
b) +3 and 0 respectively

c) +3 and -1 respectively

d) +1 and +1 respectively

Solution

5. As per IUPAC guidelines, the name of the complex [Co( en)2 ( ONO)Cl ] Cl is

a) chlorobisethylenediaminenitritocobalt(III) chloride

b) chloridobis(ethane-1,2-diamine)nitro k-Ocobaltate(III) chloride

c) chloridobis(ethane-1,2-diammine)nitrito k -Ocobalt(II) chloride

d) chloridobis(ethane-1,2-diamine)nitro k -Ocobalt(III) chloride

6. IUPAC name of the complex K3 [Al ( C2O4 )3 ] is

a) potassiumtrioxalatoaluminium(III)

b) potassiumtrioxalatoaluminate(II)

c) potassiumtrisoxalatoaluminate(III)

d) potassiumtrioxalatoaluminate(III)

7. A magnetic moment of 1.73BM will be shown by one among the following

a) TiCl4

b) [CoCl6] 4-
c) [Cu (NH3)4]2+
d) [Ni (CN)4 ]2-

Solution

8. Crystal field stabilization energy for high spin d5 octahedral complex is

a) – 0.6 ∆0.

b) 0

c) 2 (P −∆0)

d) 2 (P+ ∆0)

Solution
The electronic configuration t2g3, eg2

[3x(-0.4) + 2(0.6)]Δ0

[-1.2 + 1.2]Δ0 =0

Answer : option(b)

9. In which of the following coordination entities the magnitude of Δ 0 will be

maximum?

a) [Co (CN)6]3-

b) [ Co(C2O4)3]3-
c) [Co(H2O)6]3+

d) [Co(NH3)]3+

Solution
In all the complexes, the central metal ion is Co 3+, among the given ligands CN− is
the strongest ligand, which causes large crystal field splitting i.e maximum ∅0

10. Which one of the following will give a pair of enantiomorphs?

a) [Cr(NH3)6 ] [Co(CN)6]

b) [Co( en)2 Cl2]Cl

c) [Pt (NH3)4 ] [PtCl4]

d) [Co(NH3)2 Cl2]?

Solution

Complexes given in other options (a), (c) and (d) have symmetry elements and
hence they are optically inactive.

11. Which type of isomerism is exhibited by Pt ( NH3)2 Cl2 ?

a) Coordination isomerism

b) Linkage isomerism
c) Optical isomerism

d) Geometrical isomerism

Solution

12. How many geometrical isomers are possible for [ Pt(Py)(NH 3)(Br)(Cl)] ?

a) 3

b) 4

c) 0

d) 15

Solution
Three isomers. If we consider any one of the ligands as reference ( say Py), the
arrangement of other three ligands ( NH3, Br and Cl- ) with respect to (Py) gives
three geometrical isomers.

13. Which one of the following pairs represents linkage isomers?

a) [Cu ( NH3)4] [PtCl4] and [Pt ( NH3)4] [CuCl4]

b) [Co ( NH3)5( NO3)] SO4 and [ Co (NH3)5(ONO)]

c) [Co ( NH3 )4 ( NCS)2] Cl and [Co ( NH3)4 ( SCN)2] Cl

d) both (b) and (c)

Solution

(a) coordination isomers

(b) no isomerism ( different molecular formula)

(c) ← NCS , ← SCN coordinating atom differs : linkage isomers

14. Which kind of isomerism is possible for a complex [Co ( NH3)4 Br2] Cl ?

a) geometrical and ionization

b) geometrical and optical

c) optical and ionization

d) geometrical only

Solution

For [ MA4 B2 ]n+ complexes-geometrical isomerism is possible

15. Which one of the following complexes is not expected to exhibit isomerism?

a) [Ni(NH3)4(H2O)2]2+

b) [Pt(NH3)2Cl2]

c) [Co(NH3)5SO4]Cl

d) [Fe(en)3]3+

Solution

Option (a) and (b) – geometrical isomerism is possible

Option (c) – ionization isomerism is possible

Option (d) – no possibility to show either constitutional isomerism or stereo

isomerism
16. A complex in which the oxidation number of the metal is zero is

a) K4[Fe(CN)6]

b) [Fe(CN)3(NH3)3]

c) [Fe(CO)5]

d) both (b) and (c)

Solution

(a) Fe2+

(b) Fe3+

(c) Fe0

17. Formula of tris(ethane-1,2-diamine)iron(II)phosphate

a) [Fe(CH3-CH(NH2)2)3](PO4)3

b) [Fe(H2N-CH2-CH2-NH2)3)](PO4)

c) [Fe(H2N-CH2-CH2-CH2-NH2)3](PO4)2

d) [Fe(H2N-CH2-CH2-NH2)3]3(PO4)2

Solution

[Fe (en )3]2+ (PO43-)

18. Which of the following is paramagnetic in nature?

a) [Zn(NH3)4]2+

b) [Co(NH3)6]3+

c) [Ni(H2O)6]2+
d) [Ni(CN)4]2-

Solution

(a) Zn2+ (d10 ⟹ diamagnetic)

(b) Co3+ (d6 Low spin ⟹ t2g6, eg0 diamagnetic)

(c) Ni2+ (d8 Low spin ⟹ t2g6, eg2 paramagnetic)

(d) [Ni(CN)4]2- (dsp2 ; square planar, diamagnetic)

19. Fac-mer isomerism is shown by

a) [Co(en)3]3+

b) [Co(NH3)4(Cl)2] +

c) [Co(NH3)3(Cl)2]

d) [Co(NH3)5Cl]SO4

Solution

[Co (NH3)3(Cl)3]

20. Choose the correct statement.

a) Square planar complexes are more stable than octahedral complexes

b) The spin only magnetic moment of [Cu ( Cl)4 ]2− is 1.732 BM and it has square
planar structure.

c) Crystal field splitting energy (∆0) of [FeF6]4- is higher than the (∆ 0) of [Fe
(CN)6]4-

d) crystal field stabilization energy of [V(H2O)6]2+ is higher than the crystal

field stabilization of [Ti (H2O)6]2+

Solution
V2+ ( t2g3, eg0 ; CFSE = 3 x (-0.4)Δ0 = -1.2 Δ0)

Ti2+ ( t2g2, eg0 ; CFSE = 2 x (-0.4)Δ0 = -0.8 Δ0)

Statements given in option (a) ,(b), and (c) are wrong.

The correct statements are

(a) since, the crystal field stabilization is more in octahedral field , octahedral
complexes are more stable than square planar complexes.

DISCRIPTIVE QUESTIONS
1. Write the IUPAC names for the following complexes.

i) Na2 [Ni( EDTA)]

ii) [Ag (CN)2]

iii) [Co(en)3]2 (SO4)3

iv) [Co(ONO) (NH3)5]2+

v) [Pt(NH3)2 Cl(NO2)]

2. Write the formula for the following coordination compounds.

a) potassiumhexacyanidoferrate(II)

b) pentacarbonyliron(0)

c) pentaamminenitrito −κ −N -cobalt(III)ion

d) hexaamminecobalt(III)sulphate
e) sodiumtetrafluoridodihydroxidochromate(III)

3. Arrange the following in order of increasing molar conductivity

i) Mg [Cr (NH3) (Cl)5 ]

ii) [ Cr (NH3)5 Cl ]3 [CoF6]2

iii) [Cr (NH3)3 Cl3 ]

4. Ni2+ is identified using alcoholic solution of dimethyl glyoxime. Write the

structural formula for the rosy red precipitate of a complex formed in the reaction.

5. [CuCl4 ]2− exists while [CuI4 ]2− does not exist why?

6. Calculate the ratio of [Ag+]/[Ag(NH3)2] in 0.2 M solution of NH3. If the stability

constant for the complex [Ag(NH3)2] is 1 7 x 107.

7. Give an example of coordination compound used in medicine and two examples

of biologically important coordination compounds.

8. Based on VB theory explain why [Cr (NH3)6]3+ is paramagnetic, while [Ni

(CN)4]2- diamagnetic

9. Draw all possible geometrical isomers of the complex [Co( en)2 Cl2]+ and
identify the optically active isomer.

10. [Ti ( H2O)6]3+ is coloured, while [Sc ( H2O)6 ]3+ is colourless- explain.

12. Give an example for complex of the type [Ma2 b2c2 ] where a, b, c are
monodentate ligands and give the possible isomers.

12. Give one test to differentiate [ Co (NH3)5Cl] SO4 and [ Co( NH3)5 SO4 ] Cl.

13. In an octahedral crystal field, draw the figure to show splitting of d orbitals.

14. What is linkage isomerism? Explain with an example.

15. Write briefly about the applications of coordination compounds in volumetric

analysis.

16. Classify the following ligand based on the number of donor atoms.

a) NH3 b) en c) ox2- d) triaminotriethylamine e) pyridine

17. Give the difference between double salts and coordination compounds.

18. Write the postulates of Werner’s theory.

19. [Ni ( CN)4 ]2− is diamagnetic, while [ NiCl4 ]2− is paramagnetic , explain using
crystal field theory.

20. Why tetrahedral complexes do not exhibit geometrical isomerism.

21. Explain optical isomerism in coordination compounds with an example.

22. What are hydrate isomers? Explain with an example.

23. What is crystal field splitting energy?

24. What is crystal field stabilization energy (CFSE) ?

25. A solution of [Ni (H2O)6]2+ is green, whereas a solution of [Ni (CN) 4 ]2+ is
colorless - Explain

26. Discuss briefly the nature of bonding in metal carbonyls.

27. What is the coordination entity formed when excess of liquid ammonia is
added to an aqueous solution of copper sulphate?

29. What are the limitations of VB theory?

30. Write the oxidation state, coordination number , nature of ligand, magnetic
property and electronic configuration in octahedral crystal field for the complex
K4[Mn (CN)6].

SOME- HOTS- QUESTIONS SOLVED

1. A compound known before Werner's time was Magnus' green salt, having the empirical
formula PtCl2 * 2NH3. It is actually a coordination compound comprised of a complex cation with 2+
charge and a complex anion with a 2- charge. Propose a formula which describes the coordination
for the Magnus' salt and assign the corresponding systematic name.

Magnus's salt is composed of two complex ions, thus, we probably need, at least, 2 Pt in
its molecular formula:

Let us try Pt2Cl4 * 4NH3:

 Since the chloride ligand has a charge of -1, each Pt should be in an oxidation state of 2+.
Thus, the cation can be [Pt (NH3)4]2+ and the anion can be [PtCl4]2-. An acceptable formula for
Magnus' salt is: [Pt (NH3)4] [PtCl4], tetraammineplatinum (II) tetrachloroplatinate (II).

2. Give the systematic name for the following:

(a) [Ni (H2O) 4(OH) 2] tetraaquadihydroxonickel (II)

(b) NH4 [Cr (NH3)2(NCS) 4] ammonium diamminetetraisothiocyanatochromate (III)

(c) K3 [Cr (ox) 3] potassium trioxalatochromium (III)

(d) [Cr (en) 3]3+ [Co (CN) 6]3- tris (ethylenediamine) chromium (III) hexacyanocobaltate
(III)

Please note that the complex ion is always ONE word, do not put spaces between the
name of the ligands and the name of the metal ion.

3. Give the chemical formula for the following (use brackets to indicate the coordination
sphere):

(a) Hexapyridinecobalt (III) chloride [Co (C5H5N) 6] Cl3

(b) Dichlorobis (ethylenediamine) platinum (IV) bromide [Pt (C2H8N2)2Cl2] Br2 or [Pt (en)
2 2 Br2
Cl ]

(c) Hexaamminenickel (II) tri (oxalato) chromate (II) [Ni (NH3)6]2[Cr (C2O4)3] or [Ni
(NH3)6]2[Cr (ox) 3]

(d) Tetraamminedichloroplatinum (IV) tetrachloroplatinate (II) [Pt (NH3)4Cl2] [PtCl4]

4.

(a) Draw all the geometric isomers for an MA2B4 complex.

For complexes that have six ligands, we will assume octahedral geometry.
 (b) Draw all the geometric isomers for an MA 2B2 complex in a planar arrangement. For a
tetrahedral arrangement, are geometric isomers possible?

Geometric isomers are not possible in a tetrahedral arrangement because all of the
corners of a tetrahedron are adjacent to one another.

(c) Draw all the geometric isomers for an MA3B3 complex.

 (d) Draw all the geometric isomers for an MABCD complex in a planar arrangement. Are optical
isomers possible?

Optical isomers are not possible for square planar complexes because any planar
compound will have a mirror plane containing all the atoms and a dissymmetric molecule
cannot have a mirror plane of symmetry.
 (e) Draw all the geometric isomers of [Cr (en) (NH 3)2BrCl] +. Which of these isomers also has an
optical isomer? Draw the various isomers.

I, II, IIIa and Iva are geometric isomers; I and II have mirror planes, thus, they do not
have optical isomers. IIIa/IIIb and IVa/IVb are the pairs of optical isomers.

5. The equilibrium constants (formation constants) for two nickel complexes are shown below:

[Ni (H2O) 6]2+ (aq) + 6NH3 (aq) --> [Ni (NH3)6]2+ (aq) + 6H2O (l)

Kf = 4 x 108

[Ni (H2O) 6]2+ (aq) + 3en (aq) --> [Ni (en) 3]2+ (aq) + 6H2O (l)

Kf = 2 x 1018

Although the donor atom is nitrogen in both instances, the formation constants are very
different. With (en), it is ten orders of magnitude bigger. The generally larger formation constants
for polydentate ligands are called the chelate effect. Explain this effect using concepts you have
seen earlier in this course.
 When a solvent is bound as a ligand to a transition metal ion, it loses a great degree of
freedom. The degree of randomness or entropy depends heavily on the number of free
molecules. When a chelating agent binds to a metal ion, it liberates more than one ligand
thereby increasing the number of free molecules and, consequently, the entropy of the
system.

6. The following reduction potentials are known for various 3+ first-row transition metal ions in
aqueous solution:

Mn3+ (aq) + e- --> Mn2+ (aq) EO=1.51 V

Fe3+ (aq) + e- --> Fe2+ (aq) E0=0.77 V

Co3+ (aq) + e- --> Co2+ (aq) E0=1.84 V

Explain why the reduction potential for Fe3+ is abnormally low.

H2O is a weak-field ligand, thus, in all the hexaaqua octahedral species of the above ions,
the metal is in a high-spin state. Mn3+ is d4, Fe3+ is d5, Co3+ is d6. Only Fe3+ has all its d orbitals
half-filled which are a relatively stable electronic configuration. Thus, the reduction
potential of the Fe (III) ion is less than its neighbors in the periodic table.

7. For each of the following ions, show the d orbital occupancies in both weak and strong
octahedral fields. Indicate the total number of unpaired electrons in each case.

(a) Mn2+ (b) Zn2+ (c) Cr3+ (d) Mn3+ (e) Co3+

(a) Mn2+ d5

Weak field (t2g3eg2) 5 unpaired electrons

Strong field (t2g5eg0 ) 1 unpaired electron

(b) Zn2+ d10

Weak and strong field (t2g6eg4) 0 unpaired electrons

(c) Cr3+ d3

Weak and strong field (t2g3eg) 3 unpaired electrons

(d) Mn3+ d4

Weak field (t2g3eg1) 4 unpaired electrons

 Strong field (t2g4eg0) 2 unpaired electrons

(e) Co3+ d6

Weak field (t2g4eg2) 4 unpaired electrons

Strong field (t2g6eg0) 0 unpaired electrons

8. What properties of the ligand determine the size of the splitting of the d-orbital energies in
the presence of an octahedral arrangement of ligands about a central transition metal ion? Explain.

In the crystal-field theory, it is the negative charge of the ligand which forces the d
electrons not to occupy the d orbitals (the eg orbitals) which are in the direct approach of the
ligand. The splitting of the d orbitals would therefore depend on the charge. Thus, the charge
of the ligand will affect the size of the splitting of the d orbital energies.

In addition, the shape of the ligand is likewise important. If the ligand looks more like a
rod rather than a football, it will have a greater directionality or anisotropy. A ligand that
looks more like a cigarette will tend to increase more the energy of the d orbitals in its line
of approach.

Crystal field theory cannot explain why some of the ligands that are neutral also lead to
stronger fields. One needs a more sophisticated theory which makes use of molecular
orbitals on the ligands. If a ligand has empty anti-bonding orbitals which are of the same
symmetry as the d orbitals, additional bonding occurs lowering further the energies of the
t2g orbitals. On the other hand, if the ligands have filled orbitals such as the halides,
additional overlap occurs leading to an increase in the energy of the t2g orbitals.

9. [NiCl4]2- is more likely to be tetrahedral while [Ni (CN) 4]2- is more likely to be square planar.
Explain.

One advantage a tetrahedral arrangement has over a square planar one is space. For this
reason, most first row transition metals prefer tetrahedral while the second and third-row
transition metals prefer square planar. Square planar is preferred because of the higher
splitting of the d orbitals which is advantageous when the metal ion does not have filled d
orbitals. The Crystal Field Stabilization Energy (CFSE) derived from the splitting of the d
orbital energies is greater for square planar arrangement. In a tetrahedral arrangement, no
pair of ligands is pointing at one specific d orbital. Thus, for first-row atoms such as Ni2+ (a d8
species), tetrahedral arrangement will be preferred if the ligands are large and weak-field. If
the ligands are small (more rod-like) and are strong-field, the planar arrangement will be
preferred. The chloride ion is large and it is a weak-field ligand so tetrachloronickelate (II) is
tetrahedral. The cyanide ion is small and it is a strong-field ligand so tetracyanonickelate (II)
will probably be square planar.
 10. A Cu electrode is immersed in a solution that is 1.00 M in [Cu (NH3)4]2+ and 1.00M in NH3.
When the cathode is a standard hydrogen electrode, the emf of the cell is found to be 0.08 V. What is
the formation constant for [Cu (NH3)4]2+?

The process is:

(A) 2H+(aq) + Cu(s) + 4NH3(aq) --> H2(g) + [Cu(NH3)4]2+

E = E0 - RT/nF (ln Q)

Q = 1; E = E0 = 0.08 V

The above process (A) can be written as (I+II+III):

I. 2H+ (aq) + 2e- --> H2 (g)

II. Cu(s) --> Cu2+ (aq) + 2e-

III. Cu2+ (aq) + 4NH3 (aq) --> [Cu (NH3)4]2+ (aq)

The reduction potentials relate to each other:

EA = EI + EII + EIII

EA is known from the experiment, 0.08 V.

EI is 0.00 V (hydrogen reference)

EII is -0.337 V (the negative of the standard reduction potential of Cu (II))

Thus, EIII should be 0.417 V.

E0 = (0.0592/2) log Kf

log Kf = 2 (0.417)/0.0592

Kf = 1.2 x 1014

SOME MORE –HOTS- QUESTIONS SOLVED

1. Werner also studied the electrical conductance of aqueous solutions containing a series of
platinum (IV) complexes having the general formula Pt (NH3) xCl4, where x is an integer that varied
from 2 to 6. His results can
be summarized as:

Number of ions produced upon complete

Formula of Complex
dissociation
Pt(NH3)6Cl4 5
Pt(NH3)5Cl4 4
Pt(NH3)4Cl4 3
Pt(NH3)3Cl4 2
Pt(NH3)2Cl4 0

Assuming that Pt(IV) forms octahedral complexes, (a) write the formulas for the five
compounds based on the dissociation results, (b) draw three-dimensional sketches of the
complexes, (include isomers that are possible), and (c) name each compound.

(a)
Rewritten Formula (showing the
Formula of Complex
coordinating ligands)
Pt(NH3)6Cl4 [Pt(NH3)6]Cl4
Pt(NH3)5Cl4 [Pt(NH3)5Cl]Cl3
Pt(NH3)4Cl4 [Pt(NH3)4Cl2]Cl2
Pt(NH3)3Cl4 [Pt(NH3)3Cl3]Cl
Pt(NH3)2Cl4 [Pt(NH3)2Cl4]

(b) and (c):

With 4 Cl- as counter ions, hexaammineplatinum (IV) chloride

 With 3 Cl- as counter ions, pentaamminechloroplatinum (IV) chloride

With 2 Cl- as counter ions, tetraamminedichloroplatinum (IV) chloride

with 1 Cl- as counter ion, triamminetrichloroplatinum(IV) chloride

Diamminetetrachloroplatinum (IV)

2. Crystal Field Theory fails in explaining why a neutral ligand such as CO can cause a very large
crystal field splitting. Use Molecular Orbital Theory to explain why the CO ligand leads to a higher
crystal field splitting.

In Molecular Orbital Theory, the crystal field splitting is related to the difference
between the energy of the t2g and eg orbitals. The t2g orbitals are essentially nonbonding and
are composed of the dxz, dyz and dxy orbitals. The CO molecule contains empty antibonding 
orbitals. These antibonding orbitals have the same symmetry as the t2g orbitals and since
they are empty, these additional overlap (see figure below) will lead to a lowering in energy
of the t2g orbitals:

The t2g orbitals lower in energy but the eg orbitals (since they do not overlap with the 
orbital) remain the same in energy, thus, leading to an increase in the energy separation
between the t2g and eg orbitals.

4. When Pt has a coordination number of 6, an octahedral geometry is normally assumed. On

the other hand, when Pt has a coordination number of 4, a square planar geometry is observed. A
coordination compound has the empirical formula PtBr (en) (SCN) 2 and is diamagnetic. In aqueous
solution, each unit of this compound produces two complex ions. The ligand ethylenediamine (en)
is present only in the cation while Br is present only in the anion. (a) What is the molecular formula
of this compound (b) What is the formula of the complex cation? (c) The complex anion? (d) Give
the d-electron configuration (using Crystal Field Theory) of the Pt in each of the complex ions.

(a) Both Br- and SCN- have a charge of negative 1, thus, for the molecule to be neutral, Pt
needs a +3 charge. However, this will not be correct since the molecule is diamagnetic. Pt
(III) has an odd number of electrons so Pt cannot be diamagnetic if it has a charge of +3.
Thus, we will need at least 2 Pt's per molecule. This automatically agrees with the
observation that two complex ions are produced. One Pt will be +4, the other +2 (average is
then 3). The molecular formula is then Pt2Br2 (en) 2(SCN) 4.
 In the molecular formula above, from the number of ligands, one can count the number
of coordination available for the 2 Pt's. Remember, en is bidentate so each one counts twice.
2 (from the 2Br) + 4 (from 2 en) + 4 (from 4SCN) = 10. With 2 Pt's, this may be 5 for each Pt. A
coordination number of 5, however, are not popular among Pt complexes. The more likely
solution is that one Pt has a coordination of 4 (therefore, square planar) and the other Pt
having a coordination of 6 (octahedral). To solve this problem further, we need to apply
Crystal Field Theory. A coordination number of 4 and a square planar geometry (due to the
nature of the splitting of the d orbitals in a square planar field) will be preferred by a d 8
central atom. A coordination number of 6 and an octahedral geometry will be preferred by a
d6 central atom (provided that the ligands are strong field ligands). Pt (II) is d8 and, thus, will
be square planar, Pt (IV) is d6 and, thus, will be octahedral. Pt (II) will be in the complex
anion and Pt (IV) will be in the complex cation.

Cation: [Pt (en) 2(SCN) 2]2+

Anion: [Pt (Br) 2(SCN) 2]2- (cis- and trans- isomers possible)

6. The equilibrium constants (formation constants) for two nickel complexes are shown below:

[Ni(H2O)6]2+(aq) + 6NH3(aq) --> [Ni(NH3)6]2+(aq) + 6H2O(l) Kf = 4 x 108

[Ni(H2O)6]2+(aq) + 3en(aq) --> [Ni(en)3]2+(aq) + 6H2O(l) Kf = 2 x 1018

 Although the donor atom is nitrogen in both instances, the formation constants are very
different. With (en), it is ten orders of magnitude bigger. The generally larger formation constants
for polydentate ligands are called the chelate effect. Explain this effect using a concept you have
seen earlier in this course.

When a solvent is bound as a ligand to a transition metal ion, it loses a great degree of
freedom. The degree of randomness or entropy depends heavily on the number of free
molecules. When a chelating agent binds to a metal ion, it liberates more than one ligand
thereby increasing the number of free molecules and, consequently, the entropy of the
system.

7.

(a) Draw all the geometric isomers for an MA2B4 complex.

For complexes that have six ligands, we will assume octahedral geometry.

(b) Draw all the geometric isomers for an MA 2B2 complex in a planar arrangement. For a
tetrahedral arrangement, are geometric isomers possible?

Geometric isomers are not possible in a tetrahedral arrangement because

all of the corners of a tetrahedron are adjacent to one another.

(c) Draw all the geometric isomers for an MA 3B3 complex.

 (d) Draw all the geometric isomers for an MABCD complex in a planar arrangement. Are optical
isomers possible?

Optical isomers are not possible for square planar complexes because
any planar compound will have a mirror plane containing all the atoms and a
dissymmetric molecule cannot have a mirror plane of symmetry.

(e) Draw all the geometric isomers of [Cr (en) (NH 3)2BrCl] +. Which of these isomers also has an
optical isomer? Draw the various isomers.
 I, II, IIIa and IVa are geometric isomers;
I and II have mirror planes, thus, they do not have optical isomers.
IIIa/IIIb and IVa/IVb are the pairs of optical isomers.

8. The following reduction potentials are known for various 3+ first-row transition metal ions in
aqueous solution:

Mn3+(aq) + e- --> Mn2+(aq) Eo=1.51 V

Fe3+(aq) + e- --> Fe2+(aq) E0=0.77 V

Co3+ (aq) + e- --> Co2+ (aq) E0=1.84 V

Explain why the reduction potential for Fe3+ is abnormally low.

H2O is a weak-field ligand, thus, in all the hexaaqua octahedral species of the above ions,
the metal is in a high-spin state. Mn3+ is d4, Fe3+ is d5, Co3+ is d6. Only Fe3+ has all its d orbitals
half-filled which are a relatively stable electronic configuration. Thus, the reduction
potential of the Fe (III) ion is less than its neighbors in the periodic table.
 9. [NiCl4]2- is more likely to be tetrahedral while [Ni (CN) 4]2- is more likely to be square planar.
Explain.

One advantage a tetrahedral arrangement has over a square planar one is space. For this
reason, most first row transition metals prefer tetrahedral while the second and third-row
transition metals prefer square planar. Square planar is preferred because of the higher
splitting of the d orbitals which is advantageous when the metal ion does not have filled d
orbitals. The Crystal Field Stabilization Energy (CFSE) derived from the splitting of the d
orbital energies is greater for square planar arrangement. In a tetrahedral arrangement, no
pair of ligands is pointing at one specific d orbital. Thus, for first-row atoms such as Ni2+ (a d8
species), tetrahedral arrangement will be preferred if the ligands are large and weak-field.
If the ligands are small (more rod-like) and are strong-field, the planar arrangement will be
preferred. The chloride ion is large and it is a weak-field ligand so tetrachloronickelate (II) is
tetrahedral. The cyanide ion is small and it is a strong-field ligand so tetracyanonickelate
(II) will probably be square planar.