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Denticity

Number of atoms in a ligand that bond to the central atom of a coordination complex

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Through Coordination complex, Ligand and Mu (letter)

Denticity is different from hapticity because hapticity refers exclusively to ligands where the coordinating atoms are contiguous. In these cases the η ('eta') notation is used. Bridging ligands use the μ ('mu') notation.

Classes

Polydentate ligands are chelating agents and classified by their denticity. Some atoms cannot form the maximum possible number of bonds a ligand could make. In that case one or more binding sites of the ligand are unused. Such sites can be used to form a bond with another chemical species.

  • Bidentate (also called didentate) ligands bind with two atoms, an example being ethylenediamine.
  • Tridentate ligands bind with three atoms, an example being terpyridine. Tridentate ligands usually bind via two kinds of connectivity, called mer and fac. fac stands for facial, the donor atoms are arranged on a triangle around one face of the octahedron. mer stands for meridian, where the donor atoms are stretched out around one half of the octahedron. Cyclic tridentate ligands such as TACN and 9-ane-S3 bind in a facial manner.
  • Quadridentate or tetradentate ligands bind with four donor atoms, an example being triethylenetetramine (abbreviated trien). For different central metal geometries there can be different numbers of isomers depending on the ligand's topology and the geometry of the metal center. For octahedral metals, the linear tetradentate trien can bind via three geometries. Tripodal tetradentate ligands, e.g. tris(2-aminoethyl)amine, are more constrained, and on octahedra leave two cis sites (adjacent to each other). Many naturally occurring macrocyclic ligands are tetradentative, an example being the porphyrin in heme. On an octahedral metal these leave two vacant sites opposite each other.
  • Quinquidentate or pentadentate ligands bind with five atoms, an example being ethylenediaminetriacetic acid.
  • Sexidentate or hexadentate ligands bind with six atoms, an example being EDTA (although it can bind in a tetradentate manner).

High denticity ligands

Larger ions, such as the lanthanides, Ca2+, and Ba2+ prefer coordination numbers greater than 6. For firmly binding these ions, ligands of denticity greater than six are often used. One example is the triaminopentacarboxylate (APCA) derived from pentetic acid (HO2CH2N(CH2N(CH2CO2H)2)2. A related ligand is 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetate (DOTA).

The conjugate base of diethylenetriaminepentaacetic acid (DTPA) has a high affinity for metal cations. Thus, the penta-anion DTPA5− is potentially an octadentate ligand assuming that each nitrogen centre and each –COO− group counts as a centre for coordination

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