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Study Unit 3 - 3 - 2 Types of Ligands and Coordination Number

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0% found this document useful (0 votes)
33 views26 pages

Study Unit 3 - 3 - 2 Types of Ligands and Coordination Number

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tebzanelly
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We take content rights seriously. If you suspect this is your content, claim it here.
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Ligands and

coordination number
NCHE321
Study Unit 3
Outcomes of lecture
• Learn and be able to identify the different types of ligands in
coordination compound.

• Identify and determine the coordination number within the


coordination compound.
Monodentate or unidentate ligands

• NH3, CN-, CO
• Can be a charged or neutral molecule.
• Coordinate using one electron pair
Bidentate ligands
Tridentate ligands
Quadridentate ligands
Pentadentate ligands
Macrocylclic amine ligands
Macrocyclic polyethers ligands
Some common ligands
Practice
• State the type of the following ligands:
1. triethylenetetraamine N(CH2CH2NH2)3

2. ethylenediaminetetraacetato (EDTA) (COOH)2N(CH2)N(COOH)2

3. oxalate (ox) C2O42

4. acetylacetonate (acac) CH(COCH3)2-


Coordination number (CN) and
structure
CN = number donor atoms coordinated to metal atom
The coordination number of complexes is dependent on several factors:

1. Charge of the metal and charge of the ligand


• High cation charge and small anion charge
• Electrostatic reasons – promotes high CN

2. For a specific cation- and anion radius the CN will be limited to a maximum
• A small cation can accommodate few large anions
Coordination number (CN) and
structure cont.
3. A more polarisable ligand will transfer more charge to the metal than a hard ligand
• CN will decrease
• However, if the ligand accept electrons back through back donation from the metal
the CN will increase

4. Availability of empty d orbitals could create the possibility that more ligand electrons
could be donated
• CN increases
CN 2

• Metal atom with filled d-orbitals (d10)


• example Cu+, Ag+, Au+ and Hg2+
Linear molecules
• example [H3N-Ag-NH3]+,
[NC-Ag-CN]- and [Cl-Au-Cl]-
Addition of ligands take place easily
CN 3

• Rare
• Triangular planar [HgI3]-
• Trigonal pyramidal [SnCl3]-
• Usually in complexes with very big ligands
CN 4

• Very common
• Tetrahedral complexes
• (d0 and d10): MnO4-, CrO42-, Ni(CO)4 and Cu(py)4+
• (d5): MnCl42-
• (d7): CoCl42-
CN 4 cont.

• Square plane complexes


• (d8): Ni2+, Pd2+, Pt2+, Au3+
• Examples: [Ni(CN)4]2-, [Pt(NH3)4]2+, AuF4-
• cis- and trans-isomers
• (d9): Cu2+
• Cu(H2O)42+
• Octahedral two axial coordination points
• Weakly bonded
• - not considered
• Distortion of the tetrahedral to a square plane requires little energy
CN 5

• Square pyramidal structure and Trigonalbipyramidal structure

• d1- to d9-metals
• examples VO(acac)2 and Fe(CO)5

• Only one C signal on NMR


• – exchange between structures
CN 6

• Octahedral structure
most general structural for transitional metal complex
• d0 to d10
• Octahedral distortions
little energy
CN 6 cont.

Octahedral Tetragonal distortion Rombic distortion Trigonal distortion

b
L3 L3 L3 L3
M M M M M
1 L2 L2 L1 L2 L2
L
a
L1 L1
ML1 = ML2 ML1  ML2 = ML3 ML1  ML2  ML2 ab
= ML3
CN 7

• Rare
• No structure with high symmetry
• Pentagonal pyramidal, covered octagon and the covered trigonal
prismatic structure
CN 8

• Cubic – very symmetric


• Simple compound – Example CsCl
• Distortion to square anti-prismatic structure - requires little
energy
Summary
• Different types of ligands.
• Different coordination number.
End of lecture

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