Cambridge Encyclopedia :: Cambridge Encyclopedia Vol. 46

ligand

A molecule or ion bonded to another. It is most often used to describe species bonded to the central metal ion in a co-ordination compound.

Examples of common ligands (by field strength)

In the following table the ligands are sorted by field strength (weak field ligands first):

Ligand formula (bonding atom(s) in bold) Charge Most common denticity Remark(s)
Iodide I- monoanionic monodentate
Bromide Br- monoanionic monodentate
Sulphide S2- dianionic monodentate (M=S), or bidentate bridging (M-S-M')
Thiocyanate S-CN- monoanionic monodentate ambidentate (see also isothiocyanate, vide infra
Chloride Cl- monoanionic monodentate also found bridging
Nitrate O-NO2- monoanionic monodentate
Azide N-N2- monoanionic monodentate
Fluoride F- monoanionic monodentate
Hydroxide O-H- monoanionic monodentate often found as a bridging ligand
Oxalate [O-C(=O)-C(=O)-O]2- dianionic bidentate
Water H-O-H neutral monodentate monodentate
Isothiocyanate N=C=S- monoanionic monodentate ambidentate (see also thiocyanate, vide supra)
Acetonitrile CH3CN neutral monodentate
Pyridine C5H5N neutral monodentate
Ammonia NH3 neutral monodentate
Ethylenediamine en neutral bidentate
2,2'-Bipyridine bipy neutral bidentate easily reduced to its (radical) anion or even to its dianion
1,10-Phenanthroline phen neutral bidentate
Nitrite O-N-O- monoanionic monodentate ambidentate
Triphenylphosphine PPh3 neutral monodentate
Cyanide CN- monoanionic monodentate can bridge between metals (both metals bound to C, or one to C and one to N)
Carbon monoxide CO neutral monodentate can bridge between metals (both metals bound to C)

Note: The entries in the table are sorted by field strength, binding through the stated atom (i.e.

Ligand formula (bonding atom(s) in bold) Charge Most common denticity Remark(s)
Acetylacetonate (Acac) CH3-C(O)-CH-C(O)-CH3 monoanionic bidentate In general bidentate, bound through both oxygens, but sometimes bound through the central carbon only,
see also analogous ketimine analogues
Alkenes R2C=CR2 neutral compounds with a C-C double bond
Benzene C6H6 neutral and other arenes
1,2-Bis(diphenylphosphino)ethane (dppe) Ph2PC2H4PPh2 neutral bidentate
Corroles tetradentate
Crown ethers neutral primarily for alkali and alkaline earth metal cations
2,2,2-crypt hexadentate primarily for alkali and alkaline earth metal cations
Cryptates neutral
Cyclopentadienyl [C5H5]- monoanionic
Diethylenetriamine (dien) neutral tridentate related to TACN, but not constrained to facial complexation
Dimethylglyoximate (dmgH-) monoanionic
Ethylenediaminetetraacetate (EDTA) tetra-anionic hexadentate actual ligand is the tetra-anion
Ethylenediaminetriacetate trianionic pentadentate actual ligand is the trianion
glycinate bidentate other α-amino acid anions are comparable (but chiral)
Haem dianionic tetradentate macrocyclic ligand
Nitrosyl NO+ cationic bent (1e) and linear (3e) bonding mode
Scorpionate ligand tridentate
Sulfite monoanionic monodentate ambidentate
2,2',5',2-Terpyridine (terpy) neutral tridentate meridional bonding only
Thiocyanate monoanionic monodentate ambidentate, sometimes bridging
Triazacyclononane (tacn) (C2H4)3(NR)3 neutral tridentate macrocyclic ligand
see also the N,N',N"-trimethylated analogue
Triethylenetetramine (trien) neutral tetradentate
Tris(2-aminoethyl)amine (tren) neutral tetradentate
Tris(2-diphenylphosphineethyl)amine (np3) neutral tetradentate
Terpyridine neutral tridentate
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