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Class XII ⚗️ Chemistry ~15 MCQs/year Ch 5 of 10

Coordination Compounds

CUET unit: Coordination Compounds

📌 Snapshot

  • Establishes Werner's primary/secondary valence framework that underpins all modern coordination chemistry — primary valence is ionisable, secondary valence is the coordination number and is fixed for a metal (NCERT §5.1, p. 119-120).
  • Develops the vocabulary CUET routinely tests: coordination entity, ligand (uni/di/poly/ambidentate, chelate), coordination number, coordination sphere/polyhedron, oxidation number, homoleptic vs heteroleptic (NCERT §5.2, p. 121-122).
  • Builds IUPAC nomenclature rules for mononuclear complexes — cation-first, ligands alphabetical, anion ligand "-o" ending, "-ate" suffix for anionic complex, Roman-numeral oxidation state (NCERT §5.3, p. 122-124).
  • Classifies isomerism (stereo: geometrical + optical; structural: linkage, coordination, ionisation, solvate) and bonding theories (VBT hybridisation sp³/dsp²/d²sp³/sp³d², CFT octahedral t₂g/eₑ splitting Δₒ, tetrahedral splitting Δₜ = 4/9 Δₒ, spectrochemical series, CFSE, colour from d-d transition) (NCERT §5.4-5.5, p. 125-134).
  • Closes with biological/industrial importance — chlorophyll (Mg), haemoglobin (Fe), vitamin B₁₂ (Co), cisplatin, EDTA chelation therapy, Wilkinson catalyst (NCERT §5.7, p. 136-137).

📖 Detailed Notes

2.1 Core concepts

  • Werner studied CoCl₃·xNH₃ series: 1 mol [Co(NH₃)₆]Cl₃ gave 3 mol AgCl (1:3 electrolyte), 1 mol [CoCl(NH₃)₅]Cl₂ gave 2 mol AgCl (1:2), 1 mol [CoCl₂(NH₃)₄]Cl gave 1 mol AgCl (1:1) — explaining the data needed primary (ionisable) and secondary (non-ionisable, fixed = coordination number) valences (NCERT §5.1, p. 118-119).
  • Werner's four postulates: metals show primary + secondary linkages; primary valences are ionisable and satisfied by negative ions; secondary valences are non-ionisable, equal coordination number, satisfied by neutral molecules or negative ions; secondary-linkage groups have characteristic spatial arrangement = coordination polyhedron (NCERT §5.1, p. 119).
  • Double salts (carnallite KCl·MgCl₂·6H₂O, Mohr's salt, potash alum) dissociate completely in water, whereas complex ions like [Fe(CN)₆]⁴⁻ do not dissociate into Fe²⁺ and CN⁻ — this distinguishes a complex from a double salt (NCERT §5.1, p. 120).
  • Ligands classified by donor atoms: unidentate (Cl⁻, H₂O, NH₃), didentate (en = ethane-1,2-diamine; ox = C₂O₄²⁻), polydentate (N(CH₂CH₂NH₂)₃), hexadentate (EDTA⁴⁻ binds via 2 N + 4 O); ambidentate ligands (NO₂⁻, SCN⁻) have two different donor atoms; chelate complexes (di/polydentate using ≥2 donors on the same metal) are more stable than unidentate analogues (NCERT §5.2, p. 121).
  • Coordination number = number of σ-bonded ligand donor atoms; π-bonds are NOT counted. E.g. [PtCl₆]²⁻ CN = 6; [Fe(C₂O₄)₃]³⁻ CN = 6 (since ox is didentate) (NCERT §5.2, p. 121-122).
  • Common polyhedra are octahedral (CN 6), tetrahedral and square planar (CN 4); oxidation number written as Roman numeral, e.g. Cu(I) in [Cu(CN)₄]³⁻; homoleptic = one kind of donor ([Co(NH₃)₆]³⁺); heteroleptic = more than one ([Co(NH₃)₄Cl₂]⁺) (NCERT §5.2, p. 122).
  • IUPAC naming: cation first; ligands alphabetical before metal; anionic ligand end "-o" (chlorido, cyanido, oxalato); neutral H₂O = aqua, NH₃ = ammine, CO = carbonyl, NO = nitrosyl; "bis/tris/tetrakis" with polyatomic ligands; Roman-numeral oxidation state in parentheses; metal in anionic complex ends in "-ate" (e.g. ferrate, cobaltate) (NCERT §5.3, p. 123-124).
  • Worked examples: [Cr(NH₃)₃(H₂O)₃]Cl₃ = triamminetriaquachromium(III) chloride; [Co(en)₃]₂(SO₄)₃ = tris(ethane-1,2-diamine)cobalt(III) sulphate; [Ag(NH₃)₂][Ag(CN)₂] = diamminesilver(I) dicyanidoargentate(I) (NCERT §5.3.2, p. 124).
  • Isomerism — stereoisomerism: geometrical (cis-trans in square planar [MX₂L₂], octahedral [MX₂L₄] and [MX₂(L-L)₂]; fac/mer in [Ma₃b₃] octahedral); optical isomerism (non-superimposable mirror images = enantiomers, d and l; common in octahedral with didentate ligands like [Co(en)₃]³⁺ and cis-[PtCl₂(en)₂]²⁺ but NOT in trans-[PtCl₂(en)₂]²⁺) (NCERT §5.4.1-5.4.2, p. 125-127).
  • Geometrical isomerism is impossible in tetrahedral complexes because the relative positions of the four unidentate ligands are identical with respect to each other (NCERT Example 5.4, p. 126).
  • Structural isomerism — linkage (ambidentate ligand; [Co(NH₃)₅(NO₂)]Cl₂ red −ONO vs yellow −NO₂); coordination (ligand exchange between cation/anion complex, e.g. [Co(NH₃)₆][Cr(CN)₆] vs [Cr(NH₃)₆][Co(CN)₆]); ionisation (counter ion swaps with ligand, e.g. [Co(NH₃)₅(SO₄)]Br vs [Co(NH₃)₅Br]SO₄); solvate/hydrate ([Cr(H₂O)₆]Cl₃ violet vs [Cr(H₂O)₅Cl]Cl₂·H₂O grey-green) (NCERT §5.4.3-5.4.6, p. 127-128).
  • Valence Bond Theory: metal uses (n−1)d, ns, np or ns, np, nd orbitals to give hybrids — CN 4 sp³ tetrahedral or dsp² square planar; CN 5 sp³d trigonal bipyramidal; CN 6 d²sp³ (inner orbital / low spin) or sp³d² (outer orbital / high spin) octahedral (NCERT §5.5.1 Table 5.2, p. 128).
  • VBT worked examples: [Co(NH₃)₆]³⁺ — Co³⁺ d⁶, d²sp³, diamagnetic, inner orbital low-spin; [CoF₆]³⁻ — sp³d² outer orbital, paramagnetic with 4 unpaired e⁻ high-spin; [NiCl₄]²⁻ — Ni²⁺ d⁸, sp³ tetrahedral, paramagnetic (2 unpaired); [Ni(CO)₄] — Ni(0), sp³ tetrahedral, diamagnetic; [Ni(CN)₄]²⁻ — Ni²⁺ d⁸, dsp² square planar, diamagnetic (NCERT §5.5.1, p. 129-130).
  • Limitations of VBT: assumption-heavy; no quantitative magnetic interpretation; doesn't explain colour, thermodynamic/kinetic stability; cannot predict tetrahedral vs square planar; doesn't distinguish weak vs strong ligands (NCERT §5.5.3, p. 131).
  • Crystal Field Theory: electrostatic model, ligands = point charges/dipoles, five degenerate d orbitals split in a non-spherical ligand field. Octahedral field: d_{x²−y²} and d_{z²} (eₑ, axial) rise by (3/5)Δₒ; d_{xy}, d_{yz}, d_{xz} (t₂g) fall by (2/5)Δₒ. The energy gap is Δₒ (NCERT §5.5.4(a), p. 131-132).
  • Spectrochemical series (increasing field strength): I⁻ < Br⁻ < SCN⁻ < Cl⁻ < S²⁻ < F⁻ < OH⁻ < C₂O₄²⁻ < H₂O < NCS⁻ < EDTA⁴⁻ < NH₃ < en < CN⁻ < CO (NCERT §5.5.4, p. 132).
  • For d⁴: if Δₒ < P (pairing energy) → weak field, high-spin t₂g³eₑ¹; if Δₒ > P → strong field, low-spin t₂g⁴eₑ⁰. Strong field ligands form low-spin complexes; d⁴-d⁷ are more stable in strong field than weak field (NCERT §5.5.4(a), p. 132).
  • Tetrahedral field: splitting is inverted (e set lower, t₂ higher) and Δₜ = (4/9)Δₒ — too small to force pairing, so low-spin tetrahedral complexes are rarely observed; "g" subscript dropped (no centre of symmetry) (NCERT §5.5.4(b), p. 133).
  • Colour from d-d transition: e.g. [Ti(H₂O)₆]³⁺ is d¹; absorbs blue-green light at 498 nm (t₂g¹eₑ⁰ → t₂g⁰eₑ¹) and appears violet (complementary). Without ligand field there is no splitting → no colour: anhydrous CuSO₄ is white, CuSO₄·5H₂O is blue (NCERT §5.5.5, p. 133-134).
  • Limitations of CFT: anionic ligands ought to split most strongly (point-charge logic) but in fact sit at the low end of the spectrochemical series; covalent ligand-metal character is ignored — addressed by LFT/MOT (NCERT §5.5.6, p. 135).
  • Metal carbonyls: Ni(CO)₄ tetrahedral, Fe(CO)₅ trigonal bipyramidal, Cr(CO)₆ octahedral; Mn₂(CO)₁₀ two square-pyramidal units joined by Mn–Mn; Co₂(CO)₈ has Co–Co bond bridged by 2 CO. M–C bond has σ + π character — σ from CO lone pair into vacant metal orbital, π from filled metal d into vacant π* of CO = synergic bonding (NCERT §5.6, p. 135-136).
  • Importance — qualitative/quantitative analysis (EDTA, DMG, cupron); hardness of water by Na₂EDTA titration; extraction of gold/silver via [Au(CN)₂]⁻ and Zn displacement; purification of Ni via [Ni(CO)₄]; biology: chlorophyll (Mg), haemoglobin (Fe), vitamin B₁₂ cyanocobalamine (Co), carboxypeptidase A, carbonic anhydrase; Wilkinson catalyst [(Ph₃P)₃RhCl] for alkene hydrogenation; electroplating from [Ag(CN)₂]⁻ and [Au(CN)₂]⁻; photographic fixing as [Ag(S₂O₃)₂]³⁻; chelate therapy — D-penicillamine and desferrioxime B for excess Cu/Fe, EDTA for lead poisoning, cis-platin for tumours (NCERT §5.7, p. 136-137).

2.2 Definitions to memorise

Term Definition Page
Coordination entity Central metal atom/ion bonded to a fixed number of ions/molecules, e.g. [CoCl₃(NH₃)₃] 121
Central atom/ion Atom/ion in the entity to which a fixed number of ions/groups are bound in a definite geometry; acts as Lewis acid 121
Ligand Ion/molecule bound to the central atom in a coordination entity 121
Unidentate Ligand bound through a single donor atom (Cl⁻, H₂O, NH₃) 121
Didentate Ligand binding through two donor atoms (en, C₂O₄²⁻) 121
Polydentate Ligand with several donor atoms (e.g. N(CH₂CH₂NH₂)₃); EDTA⁴⁻ is hexadentate 121
Ambidentate Ligand with two different donor atoms, only one of which ligates at a time (NO₂⁻, SCN⁻) 121
Chelate ligand Di/polydentate ligand simultaneously using ≥2 donor atoms on the same metal; chelate complexes are more stable than unidentate analogues 121
Denticity Number of ligating groups of a chelate ligand 121
Coordination number Number of σ-bonded ligand donor atoms attached to the central metal (π bonds not counted) 121-122
Coordination sphere Central atom + attached ligands enclosed in square brackets; ions outside are counter ions 122
Coordination polyhedron Spatial arrangement of ligand donor atoms about the central metal — octahedral, tetrahedral, square planar 122
Oxidation number Charge the central atom would carry if ligands were removed with their shared electron pairs; Roman numeral in parentheses 122
Homoleptic Metal bound to only one kind of donor (e.g. [Co(NH₃)₆]³⁺) 122
Heteroleptic Metal bound to more than one kind of donor (e.g. [Co(NH₃)₄Cl₂]⁺) 122
Enantiomers Non-superimposable mirror image optical isomers; d (right-rotating) and l (left-rotating) 126
Crystal field splitting Δₒ Energy separation between eₑ and t₂g sets in octahedral field; eₑ rises by (3/5)Δₒ, t₂g falls by (2/5)Δₒ 131-132
Spectrochemical series Experimental ordering of ligands by field strength: I⁻ < Br⁻ < SCN⁻ < Cl⁻ < S²⁻ < F⁻ < OH⁻ < C₂O₄²⁻ < H₂O < NCS⁻ < EDTA⁴⁻ < NH₃ < en < CN⁻ < CO 132
Pairing energy P Energy required to pair two electrons in a single orbital 132
Synergic bonding σ donation from ligand to metal + π back-donation from metal d to ligand π* (in metal carbonyls) 136

2.3 Diagrams / processes to remember

  • Fig. 5.1 — Shapes of coordination polyhedra (octahedral, square planar, tetrahedral) with M and unidentate L (p. 122).
  • Fig. 5.2 / 5.3 / 5.4 — cis-trans isomers of [Pt(NH₃)₂Cl₂], [Co(NH₃)₄Cl₂]⁺, [CoCl₂(en)₂] (p. 125-126).
  • Fig. 5.5 — fac and mer isomers of [Co(NH₃)₃(NO₂)₃] (p. 126).
  • Fig. 5.6 / 5.7 — Optical d/l isomers of [Co(en)₃]³⁺ and cis-[PtCl₂(en)₂]²⁺ (p. 126).
  • Fig. 5.8 — Octahedral d-orbital splitting diagram with t₂g lower (by 2/5 Δₒ) and eₑ upper (by 3/5 Δₒ) (p. 132).
  • Fig. 5.9 — Tetrahedral d-orbital splitting (inverted, e lower, t₂ upper, Δₜ = 4/9 Δₒ) (p. 133).
  • Fig. 5.10 — d¹ electron transition t₂g¹eₑ⁰ → t₂g⁰eₑ¹ explaining violet colour of [Ti(H₂O)₆]³⁺ (p. 134).
  • Fig. 5.11 — Colour change as en progressively replaces H₂O in [Ni(H₂O)₆]²⁺ → [Ni(en)₃]²⁺ (green → pale blue → blue/purple → violet) (p. 134).
  • Fig. 5.13 — Structures of Ni(CO)₄, Fe(CO)₅, Cr(CO)₆, Mn₂(CO)₁₀, [Co₂(CO)₈] (p. 136).
  • Fig. 5.14 — Synergic bonding (σ ligand → metal + π metal → ligand π*) in carbonyls (p. 136).

2.4 Common confusions / NTA trap points

  • Coordination number counts σ-bonded donor atoms only, NOT the number of ligand molecules: en is didentate, so [Co(en)₃]³⁺ has CN = 6, not 3 (NCERT p. 121-122).
  • In tetrahedral complexes geometrical isomerism is NOT possible because all four ligands are equivalent in spatial relation; tetrahedral complexes also rarely show low-spin behaviour because Δₜ = (4/9)Δₒ is below pairing energy (p. 126, 133).
  • Inner orbital / low spin / spin paired (d²sp³, uses (n−1)d) vs outer orbital / high spin / spin free (sp³d², uses nd): same magnetic moment label can confuse — strong-field ligand (CN⁻, CO) gives inner orbital, weak-field (F⁻, Cl⁻, H₂O) gives outer orbital (p. 129-131).
  • NCERT spectrochemical series places anionic ligands (I⁻, Br⁻, Cl⁻, F⁻) at the WEAK end and neutral CO, CN⁻ at the strong end — this contradicts CFT's pure point-charge logic and is one of CFT's stated limitations (p. 132, 135).
  • Ionisation isomers and coordination isomers are both "structural" but differ in mechanism — ionisation swaps a ligand with the counter ion of the SAME complex ([Co(NH₃)₅(SO₄)]Br vs [Co(NH₃)₅Br]SO₄), whereas coordination isomers exchange ligands between TWO complex ions of different metals ([Co(NH₃)₆][Cr(CN)₆] vs [Cr(NH₃)₆][Co(CN)₆]) (p. 127-128).
  • "g" subscript (t₂g, eₑ) is used only for centrosymmetric geometries — octahedral and square planar — NOT for tetrahedral, whose levels are written as e and t₂ (p. 133).
  • EAN rule — Effective Atomic Number = Z − ox. state + 2×CN; classical EAN noble-gas configurations rationalise CN choices but EAN is not always obeyed (NCERT mentions historical relevance).
  • Chelate effect — Polydentate (en, EDTA) complexes are more stable than monodentate analogues of equal donor count due to entropy gain on ring formation (p. 138).

2.5 Quick reference table — coordination chemistry essentials

# Item Formula / Detail Page
1 Primary valence Oxidation state of metal 120
2 Secondary valence Coordination number 120
3 Δₜ vs Δₒ Δₜ = (4/9) Δₒ 133
4 Spin-only μ μ = √[n(n+2)] BM 130
5 Octahedral splitting t₂g (−0.4Δₒ) / eₑ (+0.6Δₒ) 133
6 Tetrahedral splitting e (lower) / t₂ (upper) 133
7 Strong-field ligands CO, CN⁻, NO₂⁻ 132
8 Weak-field ligands I⁻, Br⁻, Cl⁻, F⁻ 132
9 Inner-orbital complex d²sp³ low-spin (e.g. [Co(NH₃)₆]³⁺) 129
10 Outer-orbital complex sp³d² high-spin (e.g. [CoF₆]³⁻) 129
11 Square planar examples [Ni(CN)₄]²⁻, [PtCl₄]²⁻ 131
12 Tetrahedral examples [NiCl₄]²⁻, [MnBr₄]²⁻ 131
13 Cis-trans isomerism Octahedral MA₄B₂ & square planar MA₂B₂ 126
14 Optical isomerism [Co(en)₃]³⁺, cis-[Co(en)₂Cl₂]⁺ 127
15 Biological complexes Haemoglobin (Fe-porphyrin), chlorophyll (Mg-porphyrin), B₁₂ (Co), cisplatin (Pt) 138

🎯 Practice MCQs

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Q1. According to Werner's theory of coordination compounds, the secondary valence of a metal is equal to its:

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Answer: C

Werner's third postulate states that the secondary valence is non-ionisable and equals the coordination number, fixed for a metal. Primary valence (option A) is the oxidation state and is ionisable — not the same idea.

Q2. Which of the following pairs correctly identifies the type of ligand?

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Answer: C

EDTA⁴⁻ binds through 2 nitrogen and 4 oxygen donor atoms, making it hexadentate. NH₃ is unidentate, C₂O₄²⁻ is didentate, en is didentate (not ambidentate — ambidentate examples are NO₂⁻ and SCN⁻).

Q3. The IUPAC name of K₃[Fe(C₂O₄)₃] is:

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Answer: A

The cation K⁺ is named first. The complex anion has three C₂O₄²⁻ (charge −6) and total charge −3, so Fe is +3 and the anionic-complex metal takes the "-ate" suffix → ferrate(III). Hence potassium trioxalatoferrate(III).

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