12.co Ordination CompoundsExercise
12.co Ordination CompoundsExercise
32 | Co-ordination Compounds
Solved Examples
Example 1: Which of the following will give white Example 5: Write the correct formula for the following
precipitate with AgNO3 solution? coordination compounds:
(A) [Co (py)2 (H2O)2Cl2]Cl (A) CrCl3·6H2O (violet, with 3 chloride ions/unit formula)
(B) [Co (py)2H2OCl3]H2O (B) CrCl3·6H2O (light green, with 2 chloride ions/unit
formula)
Sol: (a) will give white precipitate (C) CrCl3·6H2O (dark green, with I chloride ion/unit
[Co (py)2 (H2O)2Cl2] Cl Co (py)2 (H2O)2Cl2] +Cl
+ – formula)
AgNO3 + Cl –
AgCl + NO–3 Sol: (A) [Cr (H2O)6] Cl3
(B) [CrCl (H2O)5] Cl2·H2O
Example 2: Specify the oxidation numbers of the metals
in the following coordination entities: (C) [CrCl2 (H2O)4] Cl·2H2O]
PtPt
coordination number of Pd4+ = 2 × 1 + 2 × 1 + 2 × 1 = 6.
OC
OC OO HH2N C C
2N
trans-isomer
trans-isomer
Example 2: A solution containing 2.665 g of CrCl3·6H2O
Example 9: [Cr(NH3)6] is paramagnetic while [Ni(CN)4]
3+ 2– is passed through a cation exchanger. The chloride
is diamagnetic. Why? ions obtained in solution were treated with excess of
AgNO3 to give 2.87 g of AgCl. Deduce the structure of
Sol: Electronic structure of the two complexes may be compound.
written as
Sol: Moles of Cl– ions ionized from moles of CrCl3·6H2O
[Ni (CN) 4]2–:
dsp
2
2.665
= = 0.01 Mol. Wt. of CrCl3·6H2O = 266.5
2.665
3d 4s 4p
CN CN CN CN
∴ Moles of AgCl obtained = Moles of Cl– ionized
In [Cr(NH3)6]3+, all the electrons are paired and hence it 2.87
is diamagnetic. = = 0.02
2
143.5
dsp
of Cl– on ionization.
NH3 NH3 NH3 NH3 NH3 NH3
Now, since the coordination number of Cr is 6 and
Due to presence of three unpaired electrons in only one Cl ion is attached to Cr by coordination bond
[Ni(CN)4]2–, it is paramagnetic.] or secondary valency, the compound is [CrCl· (H2O)5]
Cl2·H2O.
Example 10: [Cu(CN)4]2– is more stable complex than [CrCl·(H2O)5]Cl2·H2O [CrCl·(H2O)5]2+ + 2Cl– + H2O
[Cu(NH3)4]2+. Why?
2Cl– + 2AgNO3 2AgCl + 2NO–3
Sol: The higher stability constant K = 2× 10 for Cu 27 2+
+ 4CN– → [Cu (CN)4]2– than for [Cu(NH3)4]2+ (which is Example 3: Two compounds have empirical formula
4.5 × 1011) explains stability. Also CN– is stronger ligand corresponding to Cr(NH3)3(NO2)3. In aqueous solution,
than NH3.] one of these is a non-electrolyte while the other conducts
electricity. What is the lowest possible formula weight of
2 8. 34 | Co-ordination Compounds
the conducting reagent? What is the highest possible Example 7: The magnetic moment of [MnCl4]2– is
formula weight for the non-conducting reagent? 5.92 B.M. On the basis of its magnetic moment, write
configuration of Mn2+ in this complex.
Sol: For complex Cr (NH3)3· (NO2)3 (H2O)2, the two
structures can be written as: Sol: For an atom/ion
Cr (NO2 ) · (NH3 ) · (H2 O ) ·NO2 ·H2 O Magnetic moment (µ) = n(n + 2)
2 3 and (n = No. of unpaired electrons)
A
Given that µ = 5.92 B.M.
Cr (NO2 ) · (NH3 ) ·2 H2 O
3 3 ∴ 5.92 = n(n + 2) n=5
B
Thus is this complex Mn contains 5 unpaired electrons
A will be a conducting reagent as it will give two ions on and so its possible configuration may be
dissolving in water. B will be a non-conducting reagent
Mn2+ in [MnCl4]2– = [Ar] 3d54s0
as it will not be ionized in water.
So hybridization of Mn2+ in the given complex must be sp3.
Example 4: Write the IUPAC name of the compound 3d
5
4s 4p
[Cr(NH3)5(NCS)][ZnCl4]. Is this compound colored? Mn2+:
sp3 hybridization
Sol: Pentammineisothicyanatochromium (III)
tetrachlorozincate (II). Compound will be colored
because Cr (III) has d3 configuration and so d–d Example 8: [Ni (CN)4]2– is diamagnetic while [NiCl4]2– is
transition is possible. paramagnetic, Why?
Sol: EAN = 25 (electrons from Mn atom) + 10 (electrons Sol: CuSO4 + 4KCN K2[Cu(CN)4] + K2SO4
from five CO ligand) + 1 (electron from Mn—Mn bond)
[Cu (CN)4]2– is stable complex having
= 36
Thus, structure will be, K = 2 × 1027 and so it does not provide sufficient Cu2+
CO CO CO CO
ion to give precipitate of CuS.
OC OC
Mn Mn Example 10: What do you understand by macrocyclic
CO CO CO CO
effect?
e.g. Zn2+ complex with (I) is more stable than with (II).
NH NH NH NH
is
NH NH NH2 NH2
(II) Non-cyclic
(I) Cyclic
JEE Main/Boards
Q.5 Draw all the isomers (geometrical and optical) of: (i) K [Cr (H2O)2 (C2O4)2].3H2O
(i) [CoCl2 (en)2]+ (ii) [Co (NH3) Cl (en)2]2+ (ii) [Co (NH3)4Cl] Cl2
Q.15 What will be the correct order for the wavelengths Q.7 Which type do d-electron configuration exhibit
of absorption in the visible region for the following? both low and high spin in octahedral complexes?
[Ni (NO2)6]4–, [Ni (NH3)6]2+, [Ni (H2O)6]2+? (A) d1 (B) d4 (C) d3 (D) d2
Q.16 Why NH4+ ion does not form complexes? Q.8 Transition elements have the maximum tendency to
form complexes because
Q.17 Write the formula of the following Complex. (A) They are metals and all metal form complexes
Pentaamminechlorocobalt (III) ion (B) They contain incompletely filled d-orbitals
(C) Their charge/size ratio is quite large
Exercise 2 (D) Both (B) and (C)
Q.9 [(H2 O)5 Co – O – O – Co(H2 O)5 ]4 +
Single Correct Choice Type ( A)
↓
Q.1 Which of the following compound is not having
[(H2 O)5 Co – O – O – Co(H2 O)5 ]5 +
synergic bonding? (B)
Q.14 Which one of the following ions is colored? Previous Years’ Questions
(A) Sc3+ (B) Ti4+ (C) Zn2+ (D) V2+
Q.1 The coordination number of a central metal atom in
a complex is determined by (2004)
Q.15 Which of the following statement is correct.
(A) The number of ligands around a metal ion bonded
(A) The name of [Fe (H2O)5NO] SO4 is
by sigma and pi-bonds both.
pentaaquanitrosyliron (II) sulphate
(B) The number around a metal ion bonded by pi-bonds
(B) [Co(C2O4)3]3– does not have any unpaired electron
(C) The number of ligands around a metal ion bonded
(C) E.A.N. of [Fe (CO)2(NO)2] is 34 by sigma bonds
(D) [SnCl3]– acts as ligand where the Cl-atom as donor (D) The number of only anionic ligands bonded to the
atom. metal ion
Q.16 How many stereoisomer are possible for complex Q.2 Among the properties (i) reducing (ii) oxidizing (iii)
[Co(NH3)3Cl3] complexing, the set of properties shown by CN– ion
(A) 1 (B) 2 (C) 3 (D) 4 towards metal species is (2004)
(A) iii, i (B) ii, iii (C) i, ii (D) i, ii, iii
Q.17 In the volumetric analysis, Mohr’s salts is preferred
to ferrous sulphate because Q.3 Ammonia forms the complex ion [Cu (NH3)4]2+
(A) It is more readily oxidizable than FeSO4 with copper ions in alkaline solutions but not in acidic
solution. What is the reason for it? (2003)
(B) It is less easily oxidizable than FeSO4
(C) It can undergo both oxidation and reduction (A) In acidic solutions hydration protects copper ions
(D) It can be oxidized even in the absence of dilute H2SO4. (B) In acidic solutions protons coordinate with ammonia
molecules forming NH4+ ions and NH3 molecules are
not available
Q.18 [RhF6]5– complex ion is a
(C) In alkaline solutions insoluble Cu(OH)2 is precipitated
(A) Outer orbital complex which is soluble in excess of any alkali
(B) Inner orbital complex (D) Copper hydroxide is an amphoteric substance
(C) No outer or no inner orbital complex
(D) None of these Q.4 In the coordination compound, K4[Ni(CN)4] oxidation
state of nickel is (2003)
Q.19 Which of the following complex are tetrahedral in (A) –1 (B) 0 (C) +1 (D) +2
shape.
(A) [FeCl4]– (B) [BrF4]– Q.5 The coordination number and the oxidation state of
(C) [Cu(CN)4]3– (D) [AuCl4]– the element ‘E’ in the complex [E(en)2(C2O4)]NO2 (where
(en) is ethylene diamine) are, respectively (2008)
Q.20 How many ions are produced from the complex (A) 4 and 2 (B) 4 and 3
Co (NH3)6Cl2 in solution? (C) 6 and 3 (D) 6 and 2
(A) 6 (B) 4 (C) 3 (D) 2
Q.6 Which among the following will be named as
Q.21 The oxidation number of cobalt in K [Co (CO)4] is dibromidobis (ethylene diamine) chromium (III)
bromide (2012)
(A) +1 (B) +3 (C) –1 (D) –3
(A) [Cr (en)3] Br3 (B) [Cr (en)2Br2] Br
Q.22 Amongst the following the most stable complex is (C) [Cr (en) Br4]– (D) [Cr (en)Br2] Br
(A) [Fe (H2O6)]3+ (B) [Fe (NH3)6]3+
(C) [Fe (C2O4)3]3– (D) [FeCl6]3–
2 8. 38 | Co-ordination Compounds
Q.7 The “spin-only” magnetic moment [in units of Bohr Q.15 In Fe (CO)5, the Fe-C bond possesses (2006)
magneton, (µB)] of Ni2+ in aqueous solution would be
(A) π-character only (B) Both σ and π characters
(At. No. Ni = 28) (2006)
(C) Ionic character (D) σ-character only
(A) 2.83 (B) 4.90 (C) 0 (D) 1.73
(C) [Mn (H2O6)]2+, [Cr (H2O)6]2+ (D) [CoCl4]2–, [Fe (H2O)6]2+ (A) 6 and 2 (B) 4 and 2
(C) 4 and 3 (D) 6 and 3
Q.9 Which of the following has an optical isomer? (2009)
(A) [Co (NH3)3Cl]+ (B) [Co (en) (NH3)2]2+ Q.17 Being lesser energy difference between 5f and
6d than 4f and 5d orbitals. In which of the following
(C) [Co (H2O)4 (en)]3+ (D) [Co (en)2 (NH3)2]3+ octahedral complexes of Co (at no. 27), will the
magnitude of be the highest? (2008)
Q.10 Which of the following pairs represents linkage
3− 3−
isomers ? (2009) (A) Co ( CN) (B) Co ( C2O 4 )
6 3
(A) [Cu (NH3)4] [PtCl4] and [Pt (NH3)4] [CuCl4]
3+ 3+
(B) [Pd (P Ph3)2 (NCS)2] and [Pd (P Ph3)2(SCN)2] (C) Co (H2O ) (D) Co (NH3 )
6 6
Q.21 Which one of the following has an optical Q.26 The octahedral complex of a metal ion M3+ with
isomer? (2010) four monodentate ligands L1, L2, L3 and L4 absorb
2+ wavelengths in the region of red, green, yellow and blue,
(A) Zn ( en ) ( NH3 )2 (B) [Co ( en )3 ]3+ respectively. The increasing order of ligand strength of
the four ligands is (2014)
3+
(C) Co ( H2O )4 ( en ) (D) [ Zn ( en )2 ]2+ (A) L4 < L3 < L2 < L1 (B) L1 < L3 < L2 < L4
(C) L3 < L2 < L4 < L1 (D) L1 < L2 < L3 < L4
Q.22 Which of the following facts about the complex Q.27 The number of geometric isomers that can exist
Cr (NH ) Cl wrong? (2011)
for square planar Pt ( Cl)(py )(NH3 )(NH2OH) is
+
3 6 3
(A) The complex is paramagnetic (py = pyridine): (2015)
(B) The complex is an outer orbital complex (A) 2 (B) 3 (C) 4 (D) 6
(C) The complex gives white precipitate with silver
nitrate solution Q.28 Which of the following compounds is not colored
(D) The complex involves d sp hybridization and is
2 3 yellow? (2015)
octahedral in shape.
(A) Zn2 Fe ( CN) (B) K 3 Co (NO2 )
6 6
2+
(B) Mn (H2O )
2+
(A) Cr ( en) Br3
3 ( )
(B) Cr en Br2 Br
2 6
and Cr (H2O )
6
2+
(C) Cr ( en) Br4 ( )
−
and Fe (H2O )
2−
(D) Cr en Br2 Br (C) CoCl4
6
Q.25 Which of the following complex species in not 2+
(D) Cr (H2O )
2−
expected to exhibit option isomerism? (2013) and CoCl4
6
3+ +
(A) Co ( en)3 (B) Co ( en)2 Cl2 Q.30 Which one of the following complexes shows
optical isomerism? (2016)
+
(C) Co (NH3 )3 Cl3 (D) Co ( en)2 (NH3 )2 Cl2 (A) cis Co ( en) Cl2 Cl (B) trans Co ( en)2 Cl2 Cl
2
(C) Co (NH3 ) 4 Cl2 Cl (D) Co (NH3 )3 Cl3
2 8. 40 | Co-ordination Compounds
JEE Advanced/Boards
Q.7 Writ the IUPAC name of [Co (en)2Cl2] Cl and draw Q.19 What is spectrochemical series? Explain the
the structures of all the isomers with this formula of difference between a weak field ligand and a strong
complex. field ligand.
Q.8 Draw diagram to show crystal field splitting in a Q.20 What is crystal field splitting energy? How does
tetrahedral crystal field the magnitude of ∆o decide the actual configuration of
d orbital in a coordination entity?
Q.25 Write the formulas for the following coordination Q.6 Select the correct statement.
compounds:
(A) CO bond order in bridging carbonyl group is found
(i) Tetraaminequachloridocobalt (III) chloride to be lower than in that terminal carbonyl group in
(ii) Potassium tetrahydroxozincate (II) Fe2(CO)9.
(iii) Potassium trioxalatoaluminate (III) (B) Bond angle in NO2 < Bond angle in NO2–
(iv) Dichloridobis (ethane-1, 2-diamine) cobalt (III) (C) CO is a σ donor as well as π acceptor ligand.
(v) Tetracrabonylnickel (0). (D) NO is the only σ donor ligand.
Q.1 Select the correct order of C—O bond order in (C) [Cu (NH3)4]2+ (D) [Co (dmg)2]º
following complexes.
(A) [M (CO3(PCl3)2(PMe3)] > [M(CO)3(PCl3)3] > [M(CO)3(PCl3) Q.8 Which one of the following statements is incorrect
(PMe3)2] about transition elements?
(B) [M(CO)3(PCl3)2(PMe3)2] > [M(CO)3(PCl3)3] > [M(CO)3 (A) The last electron enters in the d-orbital
(PCl3)2(PMe3)]
(B) Their properties are in between those of s-block
(C) [M(CO)3(PCl3)(PMe3)2] = [M(CO)3(PCl3)3] < [M(CO)3 elements and p-block elements
(PCl3)2(PMe3)] (C) The transition element with smallest atomic number
(D) [M (CO)3(PCl3)3] > [M(CO3(PCl3)2(PMe3)] > [M(CO)3 is scandium
(PCl3)(PMe3)2] (D) Lanthanum is not a transition element but is a
lanthanide.
Q.10 Which of the following complex (s) is/are low spin Q.17 Which of the following ligand can show linkage
isomerism?
(A) K4 [Fe (CN)6] (B) [PtCl4]2–
(C) [Co (C2O4)3]
3–
(D) [Ni (NH3)6]2+ (A) NMe3 (B) O CN (C) SO42– (D) None of these
Q.11 Which of the following molecules have same Q.18 Which of the following ligand can show linkages
number of unpaired electrons. isomerism?
(A) [Cu (NH3)6]2+ (B) [Ti (H2O)6]3+ (A) It increase the stability of complex.
(C) K4 [Fe (CN)6O2] (D) [Cr (NH3)6]3+ (B) It increase the strength of metal–ligand bond.
(C) More negative charge on the central atom causes
Q.12 Which of the following type of complex (s) do/ more extent of synergic bonding.
does not produce optically active isomer (s). (D) All of these
(A) MA2B2C2 (B) MA4B2
(C) MA3B2C (D) MA2B2CD Q.19 Choose the incorrect statement from the following
options.
Q.13 For which of the complex, the E.A.N. of the central (A) C2H2 can acts as π-acid ligand
atom of the complex obeys Sidgwick E.A.N. rule. (B) [MA3B2C]n±: All isomers are optically inactive.
(A) [Ti (σ–C5H5)5]2 (B) [Fe(NO)2(CO)2] (C) [MABCDE2]n± complex has total 12 optically active
isomer
(C) [Ag(CN)2]– (D)[Hg(SCN)4]2–
(D) All statements are incorrect.
Note: AA,AB, a, b, c, d are not having chiral center. Q.5 The IUPAC name of [Ni (NH3)4] [NiCl4] is (2008)
(A) Tetrachloronickel (II)-tetraamminenickel (II)
Q.26
(B) Tetraamminenickel (II)-tetrachloRonickel(II)
Column I Column II
(C) Tetraamminenickel (II)-tetrachloronickelate (II)
(A) Zn [Fe (CN)5NO] (p) Blue color due to charge transfer
(D) Tetrachloronickel (II)-tetraamminenickelate (0)
(B) [Fe (H2O)5NO] SO4 (q) d2sp3 hybridization
Q. 7 Among the following metal carbonyls, the C—O Q.15 NiCl2 in the presence of dimethyl glyoxime (DMG)
bond order is lowest in (2007) gives a complex which precipitates in the presence of
NH4OH, giving a bright red color. (2004)
(A) [Mn(CO)6]+ (B) [Fe(CO)5] (C) [Cr(CO)6] (D) [V(CO)6]–
(A) Draw its structure and show H-bonding
Q.8 Statement-I: The geometrical isomers of the (B) Give oxidation state of Ni and its hybridization
complex [M(NH3)4Cl2] are optically inactive.
(C) Predict whether it is paramagnetic or diamagnetic
Statement-II: Both geometrical isomers of the complex
[M(NH3)4Cl2] possess axis of symmetry. (2008)
Q.16 Statement-I: Fe (H2O )5 NO SO 4 is paramagnetic
(A) Statement-I is true, statement-II is true and
statement- II is correct explanation for statement-I. Statement-II: The Fe in Fe (H2O )5 NO SO 4 has three
unpaired electrons. (2008)
(B) Statement-I is true, statement-II is true and
statement-II is not the correct explanation for (A) Statement-I is true, statement-II is true; statement-II
statement-I. is correct explanation for statement-I
(C) Statement-I is true, statement-II is false. (B) Statement-I is true, statement-II is true; statement-II
(D) Statement-I is false, statement-II is true is NOT a correct explanation for statement-I
(C) Statement-I is true, statement-II is false
Q.9 Match the Columns (2007) (D) Statement-I is false, statement-II is true
Q.20 Match the orbital overlap figures shown in list-I Q.22 Among the complex ions,
with the description given in list-II and select the correct + 3−
answer using the code given below the lists. (2014) Co (NH2 − CH2 − CH2 − NH2 ) Cl2 , Crl2 ( C2O 4 ) ,
2
−.
( )
+
Fe (H O ) ( OH) , Fe NH ( CN )
List-I List-II 2 4 2 3 4
2+
(p) p − dπ anticoding Co (NH2 − CH2 − CH2 − NH2 ) Cl
(A) 2+
and Co (NH3 ) (H2O ) Cl2
4
the number of complex ion(s) that show(s) cis-trans
(q) d − dσ bonding isomerism is (2015)
(B)
p Q r Ss
Q.26 The geometries of the ammonia complexes of
(A) 2 1 3 4
respectively, are (2016)
(B) 4 3 1 2
(C) 2 3 1 4 (A) Octahedral, square planar and tetrahedral
(D) 4 1 3 2 (B) Square planar, octahedral and tetrahedral
Exercise 1 Exercise 1
Exercise 2
Exercise 2
Q.6 Q.8 Q.13
Q.18 Q.22 Q.4 Q.11 Q.15
Q.18 Q.29
Answer Key
JEE Main/Boards
Exercise 2
Q.22 C
JEE Advanced/Boards
Exercise 2
Q.15 B Q.16 C
Comprehension Type
Q.23 A → p; B → q, r, t; C → p, q, s; D → q, r, t Q.24 A → q, s; B → r, s; C → p, q, s
Q.25 A → s; B → p, q, r; C → p; D → q, s Q.26 A → q, s; B → r, s; C → p, q, r, t; D → q, r
Q.27 A → r; B → p; C → q; D → s
Solutions
JEE Main/Boards Cl Cl
Cl
Cl
Cl
Exercise 1 CO
CO
CO
Cl H3N NH3
(ii) [PtCl2(en)2]2+ has 2 geometrical isomers.
CO CO CO
(iii) [Cr(NH3)2 Cl2(en)] has 2 geometrical isomers. Cl Cl Cl
NH3 Cl Cl
Cl Cl
Sol 8:
3d 4s
(ii) 3+
Cr 21e-
3d 4s
2 unpaired e-
3d 4s
3d 4s
Configuration in 2nd Case 2 unpaired
no e--
unpaired e
3d 4s
no unpaired e-
Sol 10: Both the complexes have Fe2+ as the central metal ion, but H2O is weak ligand, CN– is strong ligand.
3d 4s
3d 4s
[Fe(H2O)6]2+
3d 4s
3d 4s
[Fe(CN)6]4–
Hence, no. of unpaired eΘ are different in both cases which results in different colours in dilute solutions.
Co +3 Co.no=6
(ii) [CoF4]2–
3d 4s 4p
Co +2 Co.no=4
Cr +3 Co.no=6
(iv) Mn 2+
3d 4s 4p 4d
Co.no=6
Cr +3 Co. No. = 6
2 8. 50 | Co-ordination Compounds
MM = 3(5) = 15 BM [
∴ MM = n(n + 2) BM ] where n is no. of unpaired e–
(ii) [Co(NH3)4Cl]Cl2
Tetraammine chloro Cobalt (III) Chloride
3d 4s 4p
Co +3 co. = 5
No stereo isomerism
MM = 4(6) = 24 BM
(iii) CrCl3(py)3
Trichloro Tripyridinium Chromium (III)
3d 4s
Cr +3 Co. No. = 6
Fe +3 Co. No. = 4
No Isomerism, MM = (5) 7 BM = 35 BM
Sol 13: Chelation describes a particular way that ions and molecules bind metal ions. Chelation involves the
formation or presence of two or more separate coordinate bonds between a polydentate ligand and a metal atom.
Chelate effect describes the enhanced affinity of chelating ligands for a metal ion compared to the affinity of
collection of similar non-chelating ligands for same metal.
N CH2 N CH3
Cu is stable than Cu
N CH2 N CH3
3 unpaired e– i.e. n = 3
Chem i str y | 28.51
(ii) [Fe(H2O)6]2+, H2O is weak ligand Sol 6: (D) Ni → O (zero), dsp2 hybridisation is not
3d 4s
possible.
No unpaired e– i.e. n = 0
Sol 7: d4, d5, d6, d7
(ii) Has highest magnetic moment as it has highest no.
of unpaired e– Sol 8: (D) Reasons are vacant d-orbitals and that their
−
charge to size ratio is large but not that they are metals
Sol 15: Strength of ligands → NO2 > NH3 > H2O
Sol 9: (B) In (A) charge is +4, so there is more donation
∴ Wavelength of [Ni(H2O)6]2+ > [Ni(NH3)6]2+ > [Ni(NO2)6]4– in (A) from Co to O. So B.O. in A is low. So, bond length
is A is higher.
Sol 16: NH+4 cannot form complexes due to lack of lone
pair Sol 10: (C)
a b
a
Sol 17: [Co(NH3)5Cl]2+ A b A
Only 1 Isomer Only 1
A b A b
Exercise 2
b b
Facial Meridional
Single Correct Choice Type
a b
Sol 1: (D) [CoF6]3– doesn't have synergic bonding due to
lack of empty orbitalsA in F–. b A a
Only 1 Isomer Only 1 Isomer
Sol 2: (D) CO, NH3 are
A strong ligands.
b So all are low spin A b
complexes
b b
Facial Meridional
Sol 3: (D) K[Fe(H2O)2(NCS)3NO3]
Potassium di aqua-tri-isothiocynato-nitrato Ferrate (III)
Sol 11: (B) It has 5 CN– ligands (strong) Fe2+, pairing
takes place. So, d2sp3
Sol 4: (B) Fe → 26
3d 4s 4p Sol 12: (A) IUPAC of [Cr(H2O)5ONO]Br2 Penta-aquo-
nitrito-O chromium(III) Bromide
dsp2 (Tetrahedral)
Sol 13: (B) By reduction or dimension, it can attain EAN
CO is a strong ligand. Pairing takes place. of 36. So, oxidation doesn't lead to stability.
Sol 5: (D) NO → NO+, Co2+ → Co3+ (Stable) Sol 14: (D) V2+ because of presence of unpaired e–. Rest
all have no unpaired e–.
Mn+ can form stable complex with strong ligand CO.
Sol 15: (B) Co3+ → 24
So, all are reducing agents
2 8. 52 | Co-ordination Compounds
H3 N Cl Cl NH3
Sol 4: (B) + 1 × 4 + x – 1 × 4 = 0
4 + x – 4 = 0 ⇒ x = 0 for Ni.
H3 N Cl H3 N Cl
Sol 17: (B) Mohr's salt has very high mol wt but same Sol 7: (A) Ni2+ in aqueous solution means [Ni(H2O)6]2+.
reducing points. So, its less readily oxidizable than The electronic configuration of
FeSO4 and error in calculations decrease. Ni2+(aq) :
3d
3d
Sol 18: (B) [RhF6] 3–
→ Rh 3+
4s 4p
It's low spin inner orbital complex 4s 4p 4d
4d
3 2
5s 3 sp d hybridization
4d 2
sp d hybridization
[AuCl4]–Au3+
Sol 9: (D) cis-form [Co(en)2(NH3)2]3+ has optical isomers.
2
dsp (Square Planar)
2
dsp (Square Planar)
dsp2 (Square Planar)
NH3 NH3 3+ 3+
NH3 NH3
Sol 20: (C) [Co(NH3)6]Cl2
en Co Co en
3 ions i.e. [Co(NH3)6] , 2Cl
2+ –
en en
Mirror
Sol 21: (C) K[Co(CO)4]
CO → Neutral Sol 10: (B) SCN– ion can coordinate through the sulphur
K → +1 ⇒ Co → –1 or nitrogen atom. Such possibilities give rise to linkage
isomerism in coordination compounds.
M ← SCN Thiocyanato or thiocyanato-S
Sol 22: (C) [Fe(C2O4)3]3– is most stable because of chelate
effect M ← NCS Isothiocyanato or thiocyanato-N
Chem i str y | 28.53
Sol 11: (D) 27Co2+ – 1s2 2s2 2p6 3s2 3p6 3d7 4s0 Sol 16: (D)
3d 4s 4p
en
en
Hence, the complex is inner orbital complex as it involves ∴ The complex is Co ( NH3 )6 Cl3
(n – 1)d orbitals for hybridization, 3.93 = n(n + 2) ; so
n = 3 (here n is number of unpaired electron(s)). Sol 21: (B) Only option (B) is having non-super
imposable mirror image & hence one optical isomer.
∴ [Co(NH3)5Cl]Cl2 [Co(NH3)5Cl]2++2Cl– en
3 ion +2
Zn
2Cl– + 2AgNO3 → 2AgCl + 2NO–3.
NH3
en a, b, c, d = Monodentate ligands.
en
H2O a c a c a b
M M M
H2O b d d b d c
+3
Co en 3 geometrical isomers
H2O
2+
Sol 29: (A) Each Cr (H2O )
2+
and Fe (H2O )
en 6 6
JEE Advanced/Boards
Sol 22: (B) Cr (NH3 ) Cl3 involves d2 sp3 hybridization
6
and it is an inner orbital complex. Exercise 1
Sol 24: (B) Cr ( en) Br2 Br - dibromido bis (ethylene CO24− → ligand
2
Co. no = 6
diamine)chromium(III) bromide
Octahedral and homoleptic
Sol 3: (A) The main basis of the spectrochemical series is If energy released while pairing is higher than D. We get.
the energy difference in the orbitals of the control metal
atom after coming close to the ligands. More is the ∆0, Case - I
stronger is ligand.
(B) else Case - II
NH3 Cl
Sol 4:
Py NH3 Py NH3 Cl
Py Pt NH3 Py Pt NH3 Cl Cl
Cl Pt Br Br Pt Cl Cl Cl
Br NH3 Co Co
Cl Br Br Cl
Br Pt NH3
Py Pt Cl
Py Cl dl-pair
M ONO, M NO2
Sol 11: Square planar exhibit geometric isomerism
because of possibility of 2 different locations from a
single location.
→ Coordination Isomerism
AA AA
E.g.
[Co(NH3)6] [Cr(CN)6], [CO(CN)6] [Cr(NH3)6]
MM MM
AA BB Stereo Isomerism
→ Geometrical Isomerism
It's not possible in Tetrahedral. So, it can't show b a b a
geometric isomerism
M M
[Hg(NH2)Cl] + NH4Cl
The liberated mercury renders this precipitate black Sol 17: All the bonds between and ligand are coordinate
covalent bonds.
[Fe(CN)6]4– Fe2+
(ii) [FeF6]4– Fe2+, weak ligand
3d 4s
3d 4s 4p 4d
No unpaired e–
∴ Mn2+
Sol 18: The new e– in CO enters into the anti bonding orbitals
of CO and reduces its bond order. The bond order
dx -y , dz
between M and C increase. The extent depends on no.
2 2 2
Sol 19: Spectrochemical series is a series depicting the Pt +2, Square Planar
strength of the ligands during complex formation.
(iii) [Cr(NH3)3Cl3]
Weak field ligand create small ∆o (energy difference b/w
Cr +3, Octahedral
newly formed orbitals) compared to strong field ligands.
So, pairing is not preferred against weak ligands (iv) [CoBr2(en)2]+
Co +3, Octahedral
Sol 20: It's the energy difference between the new
(v) K3[Fe(CN)6]
formed orbitals in the field of a ligand.
If ∆o is high pairing is preferable Fe +3, Octahedral
eg
Sol 23: (i) [Zn(H2O)4]2+
0 3d 4s 4p
t2g
3
sp (Tetrahedral)
for ex. if we take d6 configuration.
(ii) K2[PdCl4]
if ∆o is high is more stable
4d 5s 5p
CO
2
dsp (Square Planar)
bond
(iv) K2[Ni(CN)4]
After the formation of σ bonding. There is a possibility 3d 4s 4p
for back bonding from metals to CO.
2
dsp (Square Planar)
CO
(v) [Co(NH3)5ONO]2+
2 8. 58 | Co-ordination Compounds
3d 4s 4p Exercise 2
Single Correct Choice Type
2 3
d sp (Octahedral)
Sol 1: (D) Back bonding in PCl3 > PMe3
(vi) [Co(NH3)6]2(SO4)3
So complex having more PMe3 will save higher back
3d 4s 4p bonding to CO. So, it will have lower C–O bond order.
∴ BO of CO in.
2 3
[M(CO)3(PCl3)3] > [M(CO)3(PCl3)2PMe3] > [M(CO)3PCl3
d sp (Octahedral)
(PMe2)2]
(vii) K3[Cr(C2O4)3]
3d 4s 4p Sol 2: (B) Fe 26
3d 4s 4p
2 3
d sp (Octahedral)
2
dsp (Tetrahedral)
(viii) [Pt(NH3)6]4+
Co is a strong ligand. Pairing takes place.
5d 6s 6p
sp
3 Sol 5: (B) Mohr's salt has very high mol wt but same
(Tetrahedral)
reducing points. So, its less readily oxidizable than
FeSO4 and error in calculations decrease.
Sol 24: VBT doesn't account for the difference in
configuration with ligands of different strengths. It also
doesn't account for the colour of complexes. Multiple Correct Choice Type
Where as CFT clearly explains the configurations of Sol 6: (A, C) (A) is true because bridge CO will take e–
metals with different ligands using crystal field model pair from 2 Fe atoms.
so, that we can account for shape, colour and magnetic
properties. (B) is false.
(B) Cu3+
(C) Cu2+ Tetrahedral
Chem i str y | 28.59
a a
A b b A
Paramagnetic, Square Planar
B a a B
(D) Co
b b
b b
Paramagnetic, Square Planar
A a a A
c b b b
Sol 10: (A, B, C) [Fe(CN)6]4– → low spin as CN– is
strong
b c c c
[PtCl4]2– → Pt2+ always forms low spin even with
a a weak ligands
c c a a
3 2
sp d
b c High spin as 6 orbital are needed for hybridisation.
a a Pairing need not occur.
a b b a
Sol 11: (A, B, C) Cu2+ → 1 unpaired e–
Ti3+ → 1
c b b c
Fe3+, strong ligand → 1
c c
[Cr(NH3)6]3+ → 3
(A) Has 6 stereoisomer
(D) [M(AB)A2B2] Sol 12: (A, B, C, D) MA4B2 can't produce due to presence
of plane of symmetry.
b a
MA3B2C will also have plane of symmetry.
A a A b a
a b
B a B b
m has a plane of symmetry
b a
a c
b
2 8. 60 | Co-ordination Compounds
Sol 13: (A, C, D) (A) 22 + 4(2) = 30 Sol 18: (D) Due to synergic bonding M-L bond strength
increases, so complex stability increases More negative
(B) 26 + 2 + 4 (2) = 36 Not exists as NO+
charge of M, increases synergic bonding as more e–
(C) 46 + 2(2) = 50 pairs can be donated.
(D) 78 + 4(2) = 86 Sol 19: (C) C2H2 can act as π-acid ligand All [MA3B2C]
Isomers are optically inactive due to presence of plane
of symmetry. Complex of type [MABCDE2] has 15 active
Sol 14: (B, C, D) NO3− can't show because of no LP on
isomers
N.
O
Paragraph 2:
N - -
O-CN : :S S O Sol 20: (C) CN–, because in CO32− , OH– the e– donar.
Sol 23: A → p; B → q, r, t; C → p, q, s; D → q, r, t
a b a b a b
(A) Na[Co(CO)4] monodentate ligand Follows EAN
Sol 16: (C) M M rule M
b a c b d d c (B) c[Pt(triene)Cl2] d no EAN (80) 5 membered ring
M chelating ligand (trien)
D D B
Two optically active isomers C B B
C B B
A A A A A A A A
(B) [M(AB)b
A 2c2] A A A A A
A M B A M B M
A M M A M
A b B A M B A M C A C
A B A C A A C
A C A C
D D B
B Da A D B B
D D
B B A A
A A
B B
A A A B A B
B B
A a A A
M M M M
A b C A C B A C A C
B B
A D D A D D
A A
4 geometric, 2 optically active
A A A B
and
Sol 26: A → q, s; B → r, s; C → p, q, r, t; D → q, r
B A B B
(A) Zn[Fe(CN)5NO] d2sp3, Fe +2, So
B A
diamagnetic, NO NO +
A A A A (D) K4[Fe(CN)5O2]
M M
Fe3+ d2sp3 and paramagnetic
B B B B
(CN– is strong ligand)
A A
Sol 27: A → r; B → p; C → q; D → s
(A) No. of ions 4
(B) 3
(C) 2
(D) 5
∴C 97 (q)
2 8. 62 | Co-ordination Compounds
3
sp
Previous Years' Questions d8- configuration in weak ligand field gives sp3
hybridisation, hence tetrahedral geometry.
Sol 1: (B) Salt with least no. of unpaired electrons in
Ni2+ with H2O forms [Ni(H2O)6]2+ complex and H2O is a
d-orbital of central metal will show lowest degree of
weak ligand.
paramagnetism.
Mn2+(3d5, 5 unpaired electrons)
Sol 7: (B) (A) Mn+ = 3d54s1 in presence of CO effective
Cu2+(3d9, 1 unpaired electron) configuration = 3d54s0 Three lone pair for back bonding
Fe2+(3d6, 4 unpaired electrons) with vacant orbital of C in CO.
(B) Fe0 = 3d64s2 in presence of CO effective configuration
Ni2+(3d8, 2 unpaired electrons)
= 3d8 four lone pair for back bonding with CO.
Hence, CuSO4 · 5H2O has lowest degree of paramagnetism. (C) Cr0 = 3d54s1 Effective configuration 3d6. Three lone
pair for back bonding with CO.
Sol 2: (D) Cu2+ + CN– CuCN↓ (D) V‒ = 3d44s2 effective configuration = 3d6 three lone
CuCN + 3CN– [Cu(CN)4]3– pair for bonding with CO.
Maximum back bonding is present in Fe(CO)5 there for
CO bond order is lowest here.
Sol 3: (A) In MnO–4, Mn+7 has 3d0 configuration.
Sol 8: (B) Both statements are true. However, axis of
Sol 4: (D) [NiCl4]2– : Ni2+ (3d8) symmetry is not a criteria of optical isomerism. Optical
inactivity of the two geometrical isomers of [M(NH3)4Cl2]
(tetrahedral)
3
is due to presence of lane of symmetry.
sp -hybridisation
Cl NH3
H3N NH3 H3N Cl
8
3d 4s
M M
Under influence of weak
Lignad field
H3N NH3 H3N Cl
In all other complexes, hybridization at central metal is Cl NH3
trans cis
dsp2 and complexes have square planar geometries. (has several planes of symmetry) (has several planes of symmetry)
H3N Cl H3N Cl
2 2+ 2+
dsp (B) Pt Pt
+ (D) +
(C)
OH2 OH2
OH OH
2+ 2+
(B) Pt Pt
H3N Cl Cl NH3
2+ 8
(cis)
0
(trans)
Chem i str y | 28.63
Pt =5d 4s (Diamagnetic)
(C)
+ (D) + Sol 13:
OH2 OH2
OH2 OH2 NH3
H2O H2O
H3N NH3
Co Co
H2O OH2 H2O OH2
Cl OH2 Co
2+ 7 2+ 8
Co =3d (Paramagnetic) Ni =3d (weak field ligand, paramagnetic)
H 3N NH3 OC
NH3
d2sp3-octahedral dsp2-square planar
Sol 10:
NH3 CO
Cl PPh
H3N3 Cl NH3 CO
Rh Rh Ni
Co CO
H3N CO H3N PPh3
H 3N OC CO
NH3
NHPPh sp -tetrahedral
3
Cl 3
3
Rh
Sol 14: The spin-only magnetic moment (µ) of the
OC H 3N
3 isomers complex is 1.73 BM. It indicates that nucleus of complex,
chromium ion has one unpaired electron. So, the ligand
Sol 11: m mol of complex = 30 × 0.01 = 0.3 NO is unit positively charged.
Also, 1 mole of complex [Cr(H2O)5Cl]Cl2 gives only tow K2[Cr(NO) (CN)4 (NH3)]
moles of chloride ion when dissolved in solution Potassium ammine tetracyanonitrosonium-chromate (I)
[Cr(H2O)5Cl]Cl2 [Cr(H2O)5Cl] + 2Cl 2+ –
CrCr+1 :
+1
Hence, 0.6 m mol of Ag+ would be required for Cr(I) “under influence of strong ligand field”.
precipitation.
⇒ 0.60 m mol of Ag+ = 0.1M × V(in mL) ⇒ V = 6 mL.
2 3
d sp
octahedral
Sol 12: (i) [Ti (NO3)4] : Ti4+ (3d0) No d-electron, no d-d
transition possible, colourless.
NO
(ii) [Cu(NCCH3)]BF4 : Cu+ (3d10) All d-orbitals are NC CN
completely filled, no d-d transition possible, colourless.
(iii) [Cr(NH3)6]Cl3 : Cr3+ (3d3) Complex has allowed d-d M
transitions from t2g to eg level, hence, coloured.
NC NH3
(iv) K3[VF6] : V3+ (3d2) Complex has allowed d-d transitions CN
from t2g to eg level, hence, coloured.
Sol 15: Oxidation state of Ni is +2 and hybridization is
dsp2. µ = 0
H H
O O
(nounpaired electron). H3C N N CH3
C C
Ni
C C
N N CH3
H3C
O O
H H
2 8. 64 | Co-ordination Compounds
5
(high spin)
Case-1 3d
Sol 17: (D) Co (H2O ) 4 (NH3 )2 Cl3
(no pairing)
+
[Fe(CN)4(NH)3]‒ → will show cis trans isomerism
Sol 19: (B, D) Co (NH3 ) Cl2 and Pt (NH3 )2 (H2O ) Cl
+
4 [Co(en)2(NH3)Cl]2+ → will show cis trans isomerism
(a square planar complex) will show geometrical [Co(NH3)4(H3O)Cl]2+ → Will not show cis – trans isomerism
isomerism.
(Although it will show geometrical isomerism)
Pt (NH ) (NO ) Cl and Pt (NH3 ) Cl Br will show
3 3 3 3
ionization isomerism. Sol 23: (D)
PEt3 O
Sol 20: (C) Et3P CH3
C
Fe
(p) d − dσ bonding OC Br
CO
CH2 +3 CH2 +3
Co Co
CH2 CH2
O Cl O Cl
Cl Cl
CH2
O CH2
CH2 +3
Co
CH2
NH2 Cl
Cl