JEE Main · 2024mediumCORD-055

Given below are two statements: Statement (I): Dimethyl glyoxime forms a six membered covalent chelate when treated…

Coordination Compounds · Class 12 · JEE Main Previous Year Question

Question

Given below are two statements: Statement (I): Dimethyl glyoxime forms a six membered covalent chelate when treated with NiCl₂ solution in presence of NH₄OH. Statement (II): Prussian blue precipitate contains iron both in (+2) and (+3) oxidation states. Choose the most appropriate answer:

Options
  1. a

    Statement I is false but Statement II is true

  2. b

    Both Statement I and Statement II are true

  3. c

    Both Statement I and Statement II are false

  4. d

    Statement I is true but Statement II is false

Correct Answera

Statement I is false but Statement II is true

Detailed Solution

🧠 One Statement Correct, One Not

  • Statement I says DMG forms a six-membered covalent chelate with NiCl2\mathrm{NiCl_2}. The actual chelate ring is five-membered (Ni–N=C–C=N–Ni cycle counts five atoms, including Ni). So I is false.
  • Statement II says Prussian blue contains Fe in both +2 and +3. True — Prussian blue is Fe4III[FeII(CN)6]3xH2O\mathrm{Fe_4^{III}[Fe^{II}(CN)_6]_3 \cdot xH_2O}, a mixed-valence complex. So II is true.

Combination: I false, II true → option (1).

🗺️ Verify the DMG Chelate Ring Size

The DMG ligand is HON=C(CH3)C(CH3)=NOH\mathrm{HON{=}C(CH_3){-}C(CH_3){=}NOH} (deprotonated to give HON=C(CH3)C(CH3)=NO\mathrm{HON{=}C(CH_3){-}C(CH_3){=}NO^-} as the binding form). Each DMG⁻ binds Ni²⁺ through the two N atoms. The ring goes:

Ni → N=C → C=N → Ni

Five atoms in the ring: Ni, N, C, C, N → 5-membered. Two DMG ligands per Ni²⁺, plus stabilising O–H···O hydrogen bonds connecting the two ligand units. Final geometry: square planar.

Anchor: DMG-Ni Ring Size

DMG–Ni complex → 5-membered chelate ring × 2 → square planar → bright rosy red precipitate. JEE asks variants of this annually. Always 5.

⚠️ The "6-Membered" Common Slip

Some students count the ring as six (including a hydrogen of the H-bonded bridge). H-bonds are not counted as ring members; only formal coordinate bonds and single covalent C–C, C=N etc count. Ring size for the chelate alone = 5.

Answer: (1) Statement I is false but Statement II is true\boxed{\text{Answer: (1) Statement I is false but Statement II is true}}

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Given below are two statements: Statement (I): Dimethyl glyoxime forms a six membered covalent… (JEE Main 2024) | Canvas Classes