Q.(a) Write IUPAC names of the following coordination compounds :
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Start your 14-day free trial to unlock the full solution →Concept understanding — Coordination Compound Nomenclature
Coordination Compound Nomenclature: From Intuition to Precision
Imagine you're naming a person. You'd say "Ravi Sharma" — family name first, then given name. Coordination compounds have a similar logic, but the "family name" is the metal, and the "given names" are the groups attached to it. The rules are just a systematic way of writing that name so any chemist anywhere can draw the exact structure from it.
The Core Idea
A coordination compound has a central metal ion surrounded by molecules or ions called ligands. Think of the metal as the nucleus and ligands as planets orbiting it. The entire assembly (metal + ligands) is called the coordination sphere, and it's written inside square brackets: [Co(NH₃)₆]Cl₃.
The nomenclature rules tell you:
- What order to list things
- How to name each ligand
- How to indicate the metal's oxidation state
- How to handle the counter-ions outside the brackets
The Rules, Step by Step
1. Cation before anion (just like NaCl is sodium chloride)
If the complex ion is positive, it's named first. If it's negative, it's named last. Simple.
2. Within the coordination sphere: ligands first, then metal
This is the big rule. Ligands are named before the metal, in alphabetical order (ignoring prefixes like di-, tri-).
Alphabetical order is based on the ligand's name, not its formula. So NH₃ (ammine) comes before H₂O (aqua), even though N comes after H in the alphabet.
3. Naming ligands
| Ligand type | Name | Example |
|---|---|---|
| Neutral molecule (NH₃) | ammine | [Co(NH₃)₆]³⁺ → hexaamminecobalt(III) |
| Neutral molecule (H₂O) | aqua | [Cu(H₂O)₄]²⁺ → tetraaquacopper(II) |
| Neutral molecule (CO) | carbonyl | [Ni(CO)₄] → tetracarbonylnickel(0) |
| Negative ion (Cl⁻) | chloro | [PtCl₆]²⁻ → hexachloroplatinate(IV) |
| Negative ion (CN⁻) | cyano | [Fe(CN)₆]⁴⁻ → hexacyanoferrate(II) |
| Negative ion (OH⁻) | hydroxo | [Al(OH)₄]⁻ → tetrahydroxoaluminate(III) |
ammine (with two m's) is for NH₃ as a ligand. amine (one m) is for organic compounds like ethylamine. Don't mix them up — exam setters love this trap.
4. Prefixes for multiple ligands
Use Greek prefixes: di-, tri-, tetra-, penta-, hexa-, hepta-, octa-.
If the ligand name already contains a number (like ethylenediamine), use bis-, tris-, tetrakis- instead.
[Co(en)₃]³⁺ is tris(ethylenediamine)cobalt(III), not triethylenediaminecobalt(III). The parentheses around the ligand name are mandatory when using bis/tris/tetrakis.
5. Oxidation state of the metal
Write it in Roman numerals in parentheses right after the metal name. No space.
[Fe(CN)₆]³⁻ → hexacyanoferrate(III) (iron is in +3 state)
6. If the complex is an anion, change the metal's ending
| Metal | Anionic form |
|---|---|
| Cobalt | cobaltate |
| Copper | cuprate |
| Iron | ferrate |
| Nickel | nickelate |
| Platinum | platinate |
| Zinc | zincate |
General pattern:
[M(L)ₙ]Xₘ → cation name = [prefix-ligands]metal(oxidation state)
anion name = [prefix-ligands]metalate(oxidation state)
Worked Examples
Example 1: K₃[Fe(CN)₆]
- Cation: potassium (K⁺)
- Complex anion:
[Fe(CN)₆]³⁻ - Ligands: 6 cyano → hexacyano
- Metal: iron → ferrate (because it's an anion)
- Oxidation state: Fe is +3 (since 6 CN⁻ = -6, total charge -3, so Fe must be +3)
- Answer: Potassium hexacyanoferrate(III)
Example 2: [Co(NH₃)₅Cl]Cl₂
- Cation:
[Co(NH₃)₅Cl]²⁺ - Ligands: 5 ammine + 1 chloro → alphabetical: ammine before chloro → pentaamminechloro
- Metal: cobalt
- Oxidation state: Co is +3 (5 NH₃ neutral, 1 Cl⁻ = -1, total +2, so Co = +3) …
Why this formula?
Coordination Compound Nomenclature: Why the Rules Work
Coordination compound nomenclature isn't about a single formula — it's a system of rules built on a few core principles. Let's understand the why behind each major rule, so you never have to memorise blindly.
1. The Central Idea: Ligands as "Guests" Around a Metal "Host"
A coordination compound has a central metal atom/ion surrounded by ligands (molecules or ions that donate electron pairs). The naming reflects this relationship:
- Cation first, then anion (like normal ionic compounds)
- Ligands named before the metal (because they modify the metal's identity)
Why?
In chemistry, we name the more electropositive part first (cation). The metal-ligand complex is treated as a single unit — the ligands are "attached" to the metal, so they come first in the complex name.
2. Key Rule: Ligand Order — Alphabetical, Not by Charge
Rule: Ligands are named in alphabetical order (ignoring prefixes like di-, tri-).
Why?
- If we ordered by charge or size, the name would change every time a ligand is replaced.
- Alphabetical order is universal and unambiguous — it doesn't depend on the metal or oxidation state.
- Example:
[Co(NH₃)₄Cl₂]⁺is tetraamminedichlorocobalt(III) — "ammine" (a) before "chloro" (c).
3. Oxidation State: Why Roman Numerals?
Rule: The metal's oxidation state is written in Roman numerals in parentheses after the metal name.
Why?
- The oxidation state tells you the charge on the metal after accounting for ligand charges.
- Roman numerals avoid confusion with Arabic numbers (which are used for ligand counts).
- Example:
[Fe(CN)₆]³⁻→ hexacyanoferrate(III) — the iron is Fe³⁺, not Fe²⁺.
Derivation of oxidation state:
Let the complex charge = , ligand charges = sum of ligand charges , number of ligands = .
Then:
For [Fe(CN)₆]³⁻: CN⁻ has charge -1, so , .
4. Anionic Ligands: The "-o" Ending
Rule: Anionic ligands (negative ions) end in -o (e.g., Cl⁻ → chloro, CN⁻ → cyano, OH⁻ → hydroxo).
Why?
- This distinguishes them from neutral ligands (e.g., NH₃ → ammine, H₂O → aqua).
- The suffix -o signals "this ligand came from an anion" — crucial for charge balance.
Common examples:
| Anion | Ligand name |
|---|---|
| Cl⁻ | chloro |
| CN⁻ | cyano |
| OH⁻ | hydroxo |
| SO₄²⁻ | sulfato |
5. Neutral Ligands: Special Names
Rule: Neutral ligands keep their molecular name, except for a few with special names:
- NH₃ → ammine (not "ammonia")
- H₂O → aqua
- CO → carbonyl
- NO → nitrosyl
Why?
- "Ammine" avoids confusion with ammonia (NH₃) as a free molecule.
- These special names are historical but standardised — you must memorise them for exams.
6. Prefixes: di-, tri-, tetra-, etc.
Rule: Use Greek prefixes to indicate the number of each ligand:
- 2 → di, 3 → tri, 4 → tetra, 5 → penta, 6 → hexa
Why?
- Without prefixes,
[Co(NH₃)₆]³⁺would be "hexaamminecobalt(III)" — the "hexa" tells you there are six ammines. - For ligands with complex names (e.g., ethylenediamine), use bis-, tris-, tetrakis- to avoid confusion.
Example:
[Co(en)₃]³⁺ → tris(ethylenediamine)cobalt(III) — "tris" because "triethylenediamine" would sound like three ethylenediamine molecules (which is correct, but "tris" is clearer).
7. Anionic Complexes: The "-ate" Suffix …
Part (a): (i) Dichloridobis(ethane-1,2-diamine)cobalt(III) sulphate; (ii) Potassium trioxalatoferrate(III). Part (b): double salts dissociate fully into simple ions while complexes keep their complex ion; a didentate ligand binds through two donor atoms simultaneously (chelate) whereas an ambidentate ligand can bind through either of two different atoms, one at a time.
Rules: name the cation before the anion; within brackets name ligands alphabetically (ignoring multiplying prefixes), then the metal with its oxidation state in Roman numerals; an anionic complex takes the suffix -ate.
(i) . Cation , anion . Ligands: two chlorido () and two ethane-1,2-diamine (, neutral). Alphabetically "chlorido" precedes "ethane-1,2-diamine"; because "ethane-1,2-diamine" already contains a numeral, use bis. Oxidation state: .
-> Dichloridobis(ethane-1,2-diamine)cobalt(III) sulphate.
(ii) . Cation , anion . Ligand oxalato () x3 = trioxalato. Oxidation state: . The complex is anionic, so iron becomes ferrate.
-> Potassium trioxalatoferrate(III).
Concept understanding — Werner Coordination Theory
Werner Coordination Theory: The Idea That Changed Inorganic Chemistry
Imagine you're looking at a salt like cobalt(III) chloride. The formula is written as , and when you dissolve it in water, you expect to find and ions. But something strange happens: when you add silver nitrate (which precipitates chloride ions), only some of the chlorine comes out as silver chloride. Not all of it. And the amount that precipitates depends on how you made the compound.
This was the puzzle that faced chemists in the late 1800s. Compounds like (orange-yellow) and (purple) had the same metal and the same ligands (ammonia), but different colours, different conductivities in solution, and different numbers of chloride ions that could be precipitated. The old ideas of fixed valency couldn't explain it.
Alfred Werner proposed a radical solution in 1893. He said: a metal ion has two kinds of valency.
The Core Intuition
Think of a metal ion like a king in a castle. The king has two types of relationships:
-
Primary valency (today: oxidation state) — this is the king's royal authority. It's fixed, non-directional, and satisfied by negative ions. For cobalt(III), this is +3. It's like the king's crown: it doesn't change.
-
Secondary valency (today: coordination number) — this is the king's personal bodyguard. The king can have a fixed number of guards (usually 4 or 6) who stand in specific positions around him. These guards can be neutral molecules (like ammonia) or negative ions (like chloride). The key: these guards are directly attached to the metal, forming a stable cluster called the coordination sphere.
The revolutionary idea: the chloride ions that act as bodyguards (inside the coordination sphere) do not behave like free ions. They don't precipitate with silver nitrate. They don't conduct electricity. They are "locked" to the metal.
The Precise Statement
Werner Coordination Theory (1893)
-
Every metal atom has two types of valency:
- Primary valency (ionisable): corresponds to the oxidation state. It is satisfied by negative ions. These ions are outside the coordination sphere and behave as free ions in solution.
- Secondary valency (non-ionisable): corresponds to the coordination number. It is satisfied by neutral molecules or negative ions directly bonded to the metal. These are inside the coordination sphere and do not dissociate.
-
The secondary valencies are directional — they point to fixed positions in space around the metal, giving the complex a definite geometry (e.g., octahedral for coordination number 6, square planar for 4).
-
The primary valency is non-directional — it is just a number, not a spatial arrangement.
How It Explains the Puzzle
Take the compound (orange-yellow). Werner said:
- Cobalt has primary valency +3 (needs three negative charges to satisfy it).
- Cobalt has secondary valency 6 (can hold six ligands around it).
- The six ammonia molecules satisfy all six secondary valencies. So the chloride ions cannot be inside the coordination sphere — they must be outside, as free ions.
- Structure: . All three chlorides precipitate with .
Now take (purple):
- Again, primary valency +3, secondary valency 6.
- Five ammonia molecules satisfy five secondary valencies. One chloride ion must fill the sixth spot — it becomes a ligand inside the sphere.
- The other two chlorides are outside as free ions.
- Structure: . Only two chlorides precipitate.
The number of free ions in solution determines the conductivity and the number of precipitable chlorides. Werner's theory predicted exactly these numbers — and experiments confirmed them.
The Geometry Insight …
Why this formula?
Werner Coordination Theory: Why the Key Formulas Hold
Werner Coordination Theory (1893) revolutionized inorganic chemistry by explaining how metal ions bind ligands. Let's build the reasoning from first principles — not just memorize formulas.
1. The Core Observation: Primary vs. Secondary Valence
Werner noticed that metal compounds had two types of bonding capacity:
- Primary valence (now oxidation state): Satisfies the metal's charge — ionic in nature.
- Secondary valence (now coordination number): Determines how many ligands attach — directional, spatial in nature.
Why this distinction?
Consider (one of Werner's classic compounds).
- The compound is electrically neutral overall.
- Adding precipitates all 3 Cl⁻ as — meaning all chlorides are free ions.
- Therefore, the molecules must be directly bonded to , not the chlorides.
This forces the idea: Co has a fixed capacity for direct ligand attachment (secondary valence = 6 here), separate from its charge balance (primary valence = +3).
2. The Key Formula: Coordination Number = Number of Ligands Attached
Formula:
Why this holds:
- Werner's experiments showed that only a fixed number of ligands could be replaced without breaking the compound's identity.
- For , adding acid doesn't remove easily — they are coordinated.
- The maximum number of such tightly bound ligands is the coordination number — a property of the metal ion, not the counterions.
Derivation from data:
If you have , conductivity measurements show 4 ions in solution ( + 3 Cl⁻).
If you had , conductivity shows 3 ions.
The number of chlorides inside the coordination sphere (non-precipitable) plus those outside must sum to the total chlorides. This gives the coordination number directly.
3. The Geometry Formula: Coordination Number Determines Shape
Werner proposed that secondary valences are directed in space — leading to specific geometries.
| Coordination Number | Geometry | Why? |
|---|---|---|
| 2 | Linear | Minimizes repulsion between 2 ligands |
| 4 | Tetrahedral or Square planar | 4 points in space — two arrangements possible |
| 6 | Octahedral | 6 ligands at 90° angles — most symmetric |
Why octahedral for 6?
- 6 ligands around a central atom must be placed to maximize separation.
- The octahedron (6 vertices, all equidistant from center, 90° between adjacent bonds) is the only regular polyhedron with 6 vertices.
- This explains why is octahedral — no other arrangement gives equal bond angles and distances.
4. The Isomer Counting Formula: Why or Appears
Werner used isomer counts to confirm geometry. For an octahedral complex :
Number of geometrical isomers = 5 (not 6, not 4)
Why this formula?
- Place the two 'a' ligands: they can be cis (90°) or trans (180°).
- For each, place 'b' and 'c' in remaining positions — but symmetry reduces duplicates. …
Part (a): (i) Dichloridobis(ethane-1,2-diamine)cobalt(III) sulphate; (ii) Potassium trioxalatoferrate(III). Part (b): double salts dissociate fully into simple ions while complexes keep their complex ion; a didentate ligand binds through two donor atoms simultaneously (chelate) whereas an ambidentate ligand can bind through either of two different atoms, one at a time.
(i) Double salt vs complex compound.
| Feature | Double salt | Complex compound |
|---|---|---|
| Behaviour in water | Dissociates completely into all simple ions | Gives a complex ion + counter ions; complex ion stays intact |
| Identity in solution | Lost | Retained |
| Bonding | Only ionic bonds between the component salts | Coordinate (dative) bonds within the complex ion |
| Example | (potash alum), Mohr's salt | , |
The diagnostic test: a double salt gives the usual tests of all its ions; a complex does not give the free metal-ion test because the metal is locked inside the complex ion. …
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