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Classes of Lewis bases (Ligands)
• Monodentate Ligands - A ligand that donates only one electron pair to a single
metal
• One of the best examples is NH3.

• Bridging Ligands - A ligand that donates one or more electron pairs to two or
more metals
• Halides and hydroxide are good examples, since each possesses two or more electron pairs
on the donor atom
• As we considered before, one of the steps to forming insoluble hydroxide and oxo
compounds is the bridging of two metals in the course of hydroysis.

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Classes of Lewis bases – con’t
• Ambidentate Ligands - Ligands that possess two or more donor atoms
can act as a monodentate ligand through either donor atom, or
bridge two metals.
• The pseudohalides such as cyanide, azide and thiocyanate are good
examples.

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Denticity
• The number of potential donor interactions is called the denticity
• ligands are classified as bidentate chelating ligands (as for
ethylenediamine), hexadentate chelating ligands (as for
ethylenediaminetetraacetic acid; EDTA) and so forth.

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Chelating ligands
• ethylenediamine (on the left) yields
a five-membered ring
• acetylacetonate (on the right) yields
a six-membered ring

N O

Ni Ni

N O

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 Structures of Common Chelating Ligands

N N N N
2,2’-bipyridine (bpy) N 1,10-phenathroline (phen)
N N

terpyridine (terpy)

H2N H2N NH2 H2N NH2

NH2 N
H

ethylenediamine (en) propylenediamine (prn) diethylenetriamine (dien)

H
H2N N
N NH2 N
H
NH2 NH2
H2N
triethylenetetramine (trien)
tri(ethylenediamine)amine (tren)

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Macrocyclic ligands
• Macrocyclic Ligands - A special class of generally
tetradentate chelating ligands, where the four donor
atoms are arranged in a circular ring array, as in the
porphyrins and anes.

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 Increasing Topological Constraint

Coordination Chelation Macrocycle Effect Cryptate Effect

NH2
H2N

H H N N N
N N
H
N N N
N
H2N NH2 N N
H H
NH3

H
N NH2
H2N N
H

[Ni(H2O)6]2+ + n L ¾ [Ni(L)n(H2O)2]2+ + 4 H2O

L= NH3 en trien 2,3,2-

n= 4 2 1 1
log bn = 8.12 13.5 13.8 14.6
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