In
coordination chemistry
A coordination complex consists of a central atom or ion, which is usually metallic and is called the ''coordination centre'', and a surrounding array of bound molecules or ions, that are in turn known as ''ligands'' or complexing agents. Many ...
, clathrochelates are
ligands
In coordination chemistry, a ligand is an ion or molecule (functional group) that binds to a central metal atom to form a coordination complex. The bonding with the metal generally involves formal donation of one or more of the ligand's electro ...
that
encapsulate metal ions.
Chelating ligands bind to metals more strongly than related
monodentate ligands, and
macrocyclic ligands bind more strongly than typical chelating ligands. It follows that bi- or polymacrocyclic ligands would bind to metals particularly strongly. Clathrochelates are usually derived from bimacrocyclic ligands.
The first examples were derived from the tris(
dioximate)s of cobalt(III) and iron(II). The synthesis entails replacement of the
hydrogen-bonded proton center with or group:
:
Also well known are the clathrochelates called sepulchrates derived from
tris(ethylenediamine)cobalt(III)
Tris(ethylenediamine)cobalt(III) chloride is an inorganic compound with the formula o(en)3l3 (where "en" is the abbreviation for ethylenediamine). It is the chloride salt of the coordination complex o(en)3sup>3+. This trication was important in ...
:
:
The insertion and removal of metals from the binding pocket of clathrochelates can be very slow. For this reason, many clathrochelates are prepared by the reactions of pre-coordinated ligands. These reactions often do not directly break any metal-ligand bonds, but occur in the second coordination sphere. The slowness of the metal ion exchange enables certain experiments that would otherwise be difficult or impossible. For example, it is possible to
optically resolve the equivalent of . In the absence of the special geometry imposed by the clathrochelate, the lifetime of Co(II)-amine complexes is typically very short. In this way, this family of complexes enables studies on
self-exchange redox reactions between Co(II) and Co(III) partners that would be impossible with simpler ligand systems.
See also
*
Cryptand
References
Further reading
* {{cite book , author1=Krämer, Roland , author2=Voloshin, Yan Z. , author3=Kostromina, N. A. , title=Clathrochelates: synthesis, structure and properties , publisher=Elsevier , location=Amsterdam , year=2002 , isbn=0-444-51223-3
Coordination chemistry
Chelating agents