In chemistry, a coordination complex or metal complex, is a structure consisting of a central atom or ion (usually metallic), bonded to a surrounding array of molecules or anions (ligands, complexing agents). The atom within a ligand that is directly bonded to the central atom or ion is called the donor atom. Polydentate (multiple bonded) ligands can form a chelate complex. A ligand donates at least one pair of electrons to the central atom/ion.
The ions or molecules surrounding the central atom are called ligands. Ligands are generally bound to the central atom by a coordinate covalent bond (donating electrons from a lone electron pair into an empty metal orbital), and are said to be coordinated to the atom. There are also organic ligands such as alkenes whose pi bonds can coordinate to empty metal orbitals. An example is ethene in the complex known as Zeise's salt, K +[PtCl3(C2H4)]-.
Geometry
In coordination chemistry, a structure is first described by its coordination number, the number of ligands attached to the metal (more specifically, the number of s-type bonds between ligand(s) and the central atom). Usually one can count the ligands attached, but sometimes even the counting can become ambiguous. Coordination numbers are normally between two and nine, but large numbers of ligands are not uncommon for the lanthanides and actinides. The number of bonds depends on the size, charge, and electron configuration of the metal ion and the ligands. Metal ions may have more than one coordination number.
Typically the chemistry of complexes is dominated by interactions between s and p molecular orbitals of the ligands and the d orbitals of the metal ions. The s, p, and d orbitals of the metal can accommodate 18 electrons (see 18-Electron rule; for f-block elements, this extends to 32 electrons). The maximum coordination number for a certain metal is thus related to the electronic configuration of the metal ion (more specifically, the number of empty orbitals) and to the ratio of the size of the ligands and the metal ion. Large metals and small ligands lead to high coordination numbers, e.g. [Mo(CN)8]4-. Small metals with large ligands lead to low coordination numbers, e.g. Pt[P(CMe3)]2. Due to their large size, lanthanides, actinides, and early transition metals tend to have high coordination numbers.
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