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Complex (chemistry)

This article is about the chemical complex. For other uses of this word, see complex.

In chemistry, a complex is a structure composed of a central metal atom or ion, generally a cation, surrounded by a number of negatively charged ions or neutral molecules possessing lone pairs. A complex may also be called a coordination compound or metal complex.

The ions or molecules surrounding the metal are called ligands. A ligand that is bound to a metal ion is said to be coordinated with the ion. The process of binding to the metal ion with more than one coordination site per ligand is called chelation. Compounds that bind avidly to form complexes are thus called chelating agents (for example, EDTA).

Simple ligands like water or chlorine form only one link with the central atom and are said to be monodentate. Some ligands are capable of forming multiple links to the same metal atom, and are described as bidentate, tridentate etc. EDTA is hexadentate, which accounts for the great stability of many of its complexes.

Typically, the chemistry of complexes is dominated by interactions between s and p orbitals of the ligands and the d (or f) orbitals of the metal ions. Because of this, simple octet bonding theory fails in the case of complexes and to understand the chemistry of these systems, a deeper understanding of chemical bonding rules is necessary.

One such rule is called electron counting, or the rule of 18. Crystal field theory , introduced by Hans Bethe in 1929, is a more quantum mechanically based attempt at understanding complexes. But crystal field theory treats all interactions in a complex as ionic. Ligand field theory , introduced in 1935 and built from molecular orbital theory, can handle a broader range of complexes and can explain complexes in which the interactions are covalent. The chemical applications of group theory can aid in the understanding of crystal or ligand field theory, by allowing simple, symmetry based solutions to the formal equations.

Naming complexes

The basic procedure for naming a complex:

  1. Write the names of the ligands in alphabetical order.
    • Multiply occurring monodentate ligands receive a prefix according to the number of occurrences: di-, tri-, tetra-, penta-, or hexa. Polydentate ligands (e.g., ethylenediamine, oxalate) receive bis-, tris-, tetrakis-, etc.
    • Anions end in o. This replaces the final 'e' when the anion ends with '-ate', e.g. sulfate becomes sulfato. It replaces 'ide': cyanide becomes cyano.
    • Neutral ligands are given their usual name, with some exceptions: NH3 becomes ammine; H2O becomes aqua; CO becomes carbonyl.
  2. Write the name of the central atom/ion. If the complex is an anion, the central atom's name will end in -ate, and its Latin name will be used if available (except for mercury).
  3. If the central atom's oxidation state needs to be specified (when it is one of several possible, or zero), write it as a Roman numeral (or 0) in parentheses.


[NiCl4]2- → tetrachloronickelate (II) ion
[CuNH3Cl5]3- → amminepentachlorocuprate(II) ion
[Cd(en)2(CN)2] → dicyanobisethylenediaminecadmium(II)

Transition metals make good central ions for complexes.

To study the activity of complexes in solution, it is possible to record pH spectra which shows the interaction between complexing agent and central ion as a function of the degree of dissociation of their functional groups.

External links

Index of pH-spectra

Last updated: 10-24-2004 05:10:45