Ligands: Handwritten-Style Notes
Hey there! These are my scribbled notes on ligands from inorganic chemistry. I've thrown in some flowcharts and mind
maps to make it fun and visual. Let’s dive in!
What’s a Ligand?
Electron-rich species that donates electron pairs to a central metal atom/ion.
Think of it as a generous friend giving electrons to fill empty orbitals!
Classification of Ligands
Let’s break it down with a flowchart!
Flowchart: How to Classify Ligands
Ligands
├── Based on Charge
│ ├── Negative (e.g., Cl⁻, OH⁻)
│ ├── Neutral (e.g., H₂O, NH₃)
│ └── Positive (e.g., NO⁺, rare)
├── Based on Denticity
│ ├── Monodentate (1 donor site)
│ ├── Bidentate (2 donor sites)
│ ├── Polydentate (3+ donor sites)
│ └── Ambidentate (multiple donor sites, uses one at a time)
└── Based on Electron Donation
├── Classical (donates e⁻ only, e.g., NH₃)
└── Non-Classical (π-acid, accepts e⁻ back, e.g., CO)
1. Based on Charge ⚡
Negative Ligands: Carry a negative charge.
Examples: H⁻ (Hydride), F⁻ (Fluoride), Cl⁻ (Chloride), CN⁻ (Cyanide), C₂O₄²⁻ (Oxalate)
Note: Organic ones like CH₃⁻ (Methyl) keep their “-yl” suffix in IUPAC naming.
Neutral Ligands: No charge, just chill.
Examples: NH₃ (Ammine), H₂O (Aqua), CO (Carbonyl), PPh₃ (Triphenylphosphine)
Positive Ligands: Rare, but they exist!
Example: NO⁺ (Nitrosonium)
2. Based on Denticity
Denticity = number ofbasically, how many teeth (donor sites) a ligand has!
Mind Map: Denticity of Ligands
Ligands by Denticity
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Monodentate Bidentate Polydentate
(1 donor) (2 donors) (3+ donors)
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- H⁻, NH₃ - Oxalate (C₂O₄²⁻) - EDTA⁴⁻ (Hexadentate)
- Cl⁻, CN⁻ - Glycinate (gly) - HEDTA³⁻ (Pentadentate)
- Acetylacetonate - Diethylenetriamine
(acac) (Triadentate)
Monodentate: One donor site.
Examples: H⁻ (Hydrido), NH₃ (Ammine), Cl⁻ (Chlorido)
IUPAC naming: Negative ligands end in “-o” (e.g., Chloro), neutral have no suffix.
Flexidentate: Some can act as bidentate (e.g., SO₄²⁻, CO₃²⁻) but prefer monodentate due to unstable 4-
membered rings.
Bidentate: Two donor sites, forms 5/6-membered stable rings (chelating ligands).
Examples: C₂O₄²⁻ (Oxalate), Glycinate (gly), Acetylacetonate (acac)
Symmetrical: Same donor atoms (e.g., Oxalate).
Unsymmetrical: Different donor atoms (e.g., Glycinate).
Polydentate: 3+ donor sites, super stable complexes.
Examples: EDTA⁴⁻ (Hexadentate, 6 sites), HEDTA³⁻ (Pentadentate, 5 sites)
EDTA⁴⁻ always forms octahedral geometry with 6 coordination sites.
Ambidentate: Multiple donor sites, but only one used at a time (monodentate behavior).
Examples:
SCN⁻ (Thiocyanate-S) or NCS⁻ (Thiocyanate-N)
NO₂⁻ (Nitrite-N) or ONO⁻ (Nitrite-O)
CN⁻ (Cyanide) or NC⁻ (Isocyanide)
3. Based on Electron Donation
Classical Ligands: Only donate electron pairs to the metal.
Examples: NH₃, H₂O, OH⁻, F⁻, CH₃⁻
Form σ-bonded complexes (e.g., [FeF₆]³⁻, [Ag(NH₃)₂]⁺).
Non-Classical (π-Acid) Ligands: Donate electrons and accept electrons back via π-backbonding.
Examples: CO, NO, CN⁻, PPh₃, η⁵-C₅H₅ (Cyclopentadienyl)
Form σ- and π-bonded complexes (e.g., [Fe(CN)₆]⁴⁻) or π-bonded organometallic compounds (e.g.,
Fe(η⁵-C₅H₅)₂).
Special Ligands & Properties
Flexidentate EDTA
EDTA’s denticity changes with pH!
Ligand Form Denticity
H₄EDTA 2
H₃EDTA⁻ 3
H₂EDTA²⁻ 4
HEDTA³⁻ 5
EDTA⁴⁻ 6
In [Ca(EDTA)]²⁻:
1 N-Ca-N bond angle
6 O-Ca-O bond angles
8 N-Ca-O bond angles
Organometallic Compounds (OMCs)
Have M←C linkage (metal-carbon bond).
Examples: R-Mg-X (Grignard reagents), Zn(C₂H₅)₂, Fe(η⁵-C₅H₅)₂
Note: All OMCs are complexes, but not all complexes are OMCs.
Coordination Number (C.N.)
Total electron pairs accepted by the central metal from ligands (a.k.a. secondary valency).
Depends on the metal’s oxidation state.
Flowchart: Coordination Numbers
Metal Cation
├── Monovalent (e.g., Cu⁺, Ag⁺)
│ └── C.N. = 2, 4
├── Divalent (e.g., Ni²⁺, Zn²⁺)
│ └── C.N. = 4 (Td or Sq. pl.), 5, 6
├── Trivalent (e.g., Cr³⁺, Fe³⁺)
│ └── C.N. = 6
├── Tetravalent (e.g., Pt⁴⁺, Sn⁴⁺)
│ └── C.N. = 6
└── Others (e.g., Cr⁶⁺, Os⁸⁺)
└── C.N. = 6
Fun Fact: Zn²⁺ always has C.N. = 4 (tetrahedral), Pd²⁺ always C.N. = 4 (square planar).
Key Notes
NH₄⁺: Never acts as a ligand.
Bridging Ligands: Monodentate ligands with multiple lone pairs can bridge metals (except CO).
Donor Site Preference: In neutral ligands (e.g., CO, NO), the less electronegative atom donates.
Spectrochemical Series:
Strong Field Ligands (SFL): Contain C or N as donor (e.g., CN⁻, NH₃).
Weak Field Ligands (WFL): Others (e.g., F⁻, OH⁻).
Example Complexes:
[Cr(NH₃)₅(SO₄)]⁺: SO₄²⁻ is monodentate, C.N. = 6.
[Cr(NH₃)₄(SO₄)]⁺: SO₄²⁻ is bidentate, C.N. = 6.
Nickel Test: NiCl₂ + 2DMG → [Ni(DMG)₂]↓ (Rosy red precipitate).
Mind Map: Ligand Interactions in
Complexes
Complex Compounds
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σ-Bonded σ- and π-Bonded π-Bonded
(σ-donation) (σ + π-donation) (π-donation)
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- [FeF₆]³⁻ - [Fe(CN)₆]⁴⁻ - Fe(η⁵-C₅H₅)₂
- [Ag(NH₃)₂]⁺ - [Ag(CN)₂]⁻ - Cr(C₆H₆)₂
- M(CO)₄ - K[PtCl₃(η²-C₂H₄)]
That’s it for my ligand notes! Hope the flowcharts and mind maps make it easier to visualize. Happy studying!
