Coordination Compounds: Edge Cases and Subtle Traps (9)

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Question

Determine the oxidation state of iron and the IUPAC name of [Fe(CN)6]4[\text{Fe}(\text{CN})_6]^{4-}.

Solution — Step by Step

Cyanide (CN\text{CN}^-) has charge 1-1. There are 66 of them, contributing 6-6 total. The complex has overall charge 4-4. Let xx be the oxidation state of Fe:

x+6(1)=4    x=+2x + 6(-1) = -4 \implies x = +2

Iron is in the +2+2 state.

Order: ligand count (cyanido), then central metal name. For an anion, the metal name takes the “-ate” suffix. Fe in -ate form becomes “ferrate” (Latin root).

The IUPAC name: hexacyanidoferrate(II) or as an ion, hexacyanidoferrate(II) ion.

Final answer: Fe is in oxidation state +2+2; the complex is hexacyanidoferrate(II).

Why This Works

Naming follows a strict order: number of ligands (di-, tri-, tetra-, …, hexa-), ligand name (cyanido in modern IUPAC, formerly cyano), then the central atom. For anionic complexes, use the Latin/Greek root + “-ate” (cuprate, ferrate, plumbate, argentate, aurate). For neutral or cationic complexes, the English name stays.

The oxidation state in roman numerals goes in parentheses after the metal name.

Alternative Method

Old IUPAC (pre-2005) used “cyano” instead of “cyanido”; you might see the old name “hexacyanoferrate(II)” in older textbooks. Both are still recognised by NCERT.

For neutral complexes (no overall charge), no “-ate” suffix. For cations, also no “-ate.” Only anionic complexes get the Latin-ate ending. JEE Advanced often tests this in Match-the-Column.

Common Mistake

Students often use “iron” in the name instead of “ferrate” for an anionic complex. Anions need the Latin-derived “-ate” form: ferrate, cuprate, argentate, aurate, plumbate, stannate. Memorise the metal-to-Latin map.

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