Name : Elisabet Sabatini Sibarani

Id : 4153332007

Subject: Inorganic Chemistry III

TEMPLATE REACTION

In chemistry, a template reaction is any of a class of ligand-based reactions

that occur between two or more adjacent coordination sites on a metal center. In the
absence of the metal ion, the same organic reactants produce different products. The
term is mainly used in coordination chemistry. The template effects emphasizes the
pre-organization provided by the coordination sphere, although the coordination
modifies the electronic properties (acidity, electrophilicity, etc.) of ligands.
An early example is the dialkylation of a nickel dithiolate:

The corresponding alkylation in the absence of a metal ion would yield

polymers. Crown ethers arise from dialkylations that are templated by alkali metals.
Other template reactions include the Mannich and Schiff base condensations. The
condensation of formaldehyde, ammonia, and tris(ethylenediamine)cobalt(III) to
give a clathrochelate complex is one example.

18-Crown-6 can be synthesized by the Williamson ether synthesis using

potassium ion as the template cation
Structure of nickel-aquo nitrate complex of the ligand derived from the templated
trimerization of 2-aminobenzaldehyde

The phosphorus analogue of an aza crown can be prepared by a template

reaction. Where it is not possible to isolate the phosphine itself.

Many template reactions are only stoichiometric, and the decomplexation

of the "templating ion" can be difficult. The alkali metal-templated syntheses of
crown ether syntheses are notable exceptions. Metal Phthalocyanines are generated
by metal-templated condensations of phthalonitriles, but the liberation of metal-free
phthalocyanine is difficult.
Some so-called template reactions proceed similarly in the absence of the
templating ion. One example being the condensation of acetone and
ethylenediamine, which yields isomeric 14-membered tetraaza rings.[6] Similarly,
porphyrins, which feature 16-membered central rings, form in the absence of metal
templates.

14-membered N4 macrocyclic ligands, called Curtis macrocycles, arise from the

condensation of acetone and a nickel complex of ethylenediamine.

In a general sense, transition metal-based catalysis can be viewed as

template reactions: Reactants coordinate to adjacent sites on the metal ion and,
owing to their adjacency, the two reactants interconnect (insert or couple) either
directly or via the action of another reagent. In the area of homogeneous catalysis,
the cyclo-oligomerization of acetylene to cyclooctatetraene at a nickel(II) centre
reflects the templating effect of the nickel, where it is supposed that four acetylene
molecules occupy four sites around the metal and react simultaneously to give the
product. This simplistic mechanistic hypotheses was influential in the development
of these catalytic reactions. For example, if a competing ligand such as
triphenylphosphine were added to occupy one coordination site, then only three
molecules of acetylene could bind, and these come together to form benzene (see
Reppe chemistry).