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 ...

, a template reaction is any of a class of

ligand 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 electr ...

-based reactions that occur between two or more adjacent coordination sites on a metal center. In the absence of the

metal ion A metal (from ancient Greek, Greek μέταλλον ''métallon'', "mine, quarry, metal") is a material that, when freshly prepared, polished, or fractured, shows a lustrous appearance, and conducts electrical resistivity and conductivity, e ...

, the same organic

reactant In chemistry, a reagent ( ) or analytical reagent is a substance or compound added to a system to cause a chemical reaction, or test if one occurs. The terms ''reactant'' and ''reagent'' are often used interchangeably, but reactant specifies a ...

s produce different products. The template effects emphasizes the pre-organization provided by the

coordination sphere In coordination chemistry, the first coordination sphere refers to the array of molecules and ions (the ligands) directly attached to the central metal atom. The second coordination sphere consists of molecules and ions that attached in various ...

, although the coordination modifies the electronic properties (

acidity In computer science, ACID ( atomicity, consistency, isolation, durability) is a set of properties of database transactions intended to guarantee data validity despite errors, power failures, and other mishaps. In the context of databases, a sequ ...

electrophilicity In chemistry, an electrophile is a chemical species that forms bonds with nucleophiles by accepting an electron pair. Because electrophiles accept electrons, they are Lewis acids. Most electrophiles are positively charged, have an atom that carri ...

, etc.) of ligands. An early example is the dialkylation of a nickel dithiolate: : Busch-LindoyTempRxn

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

polymer A polymer (; Greek '' poly-'', "many" + ''-mer'', "part") is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic a ...

Crown ether In organic chemistry, crown ethers are cyclic chemical compounds that consist of a ring containing several ether groups (). The most common crown ethers are cyclic oligomers of ethylene oxide, the repeating unit being ethyleneoxy, i.e., . Impo ...

s arise from dialkylations that are templated by

alkali metal The alkali metals consist of the chemical elements lithium (Li), sodium (Na), potassium (K),The symbols Na and K for sodium and potassium are derived from their Latin names, ''natrium'' and ''kalium''; these are still the origins of the names ...

s. Other template reactions include the Mannich and

Schiff base In organic chemistry, a Schiff base (named after Hugo Schiff) is a compound with the general structure ( = alkyl or aryl, but not hydrogen). They can be considered a sub-class of imines, being either secondary ketimines or secondary aldimine ...

condensations. The condensation of

formaldehyde Formaldehyde ( , ) (systematic name methanal) is a naturally occurring organic compound with the formula and structure . The pure compound is a pungent, colourless gas that polymerises spontaneously into paraformaldehyde (refer to section F ...

ammonia Ammonia is an inorganic compound of nitrogen and hydrogen with the formula . A stable binary hydride, and the simplest pnictogen hydride, ammonia is a colourless gas with a distinct pungent smell. Biologically, it is a common nitrogenous was ...

, and tris(ethylenediamine)cobalt(III) to give a

clathrochelate In coordination chemistry, clathrochelates are ligands 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 ...

complex is one example. 18-crown-6 was synthesized using potassium ion as the template cation

The phosphorus analogue of an

aza crown In organic chemistry, an aza-crown ether is an aza analogue of a crown ether (cyclic polyether). That is, it has a nitrogen atom (amine linkage, or ) in place of each oxygen atom (ether linkage, ) around the ring. While the parent crown ethers ...

can be prepared by a template reaction. Where it is not possible to isolate the phosphine itself. Phosphacrown

Limitations

Many template reactions are only stoichiometric, and the

decomplexation In chemistry, decomplexation refers to the removal of a ligand from a coordination complex. Decomplexation is of particular interest when the ligand has been synthesized within the coordination sphere of the metal, as is often the case in organomet ...

of the "templating ion" can be difficult. The alkali metal-templated syntheses of crown ether syntheses are notable exceptions. Metal

Phthalocyanine Phthalocyanine () is a large, aromatic, macrocyclic, organic compound with the formula and is of theoretical or specialized interest in chemical dyes and photoelectricity. It is composed of four isoindole units linked by a ring of nitrogen atom ...

s are generated by metal-templated condensations of

phthalonitrile Phthalonitrile is an organic compound with the formula C6H4(CN)2, which is an off-white crystal solid at room temperature. It is a derivative of benzene, containing two adjacent nitrile groups. The compound has low solubility in water but is sol ...

s, 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. Similarly,

porphyrin Porphyrins ( ) are a group of heterocyclic macrocycle organic compounds, composed of four modified pyrrole subunits interconnected at their α carbon atoms via methine bridges (=CH−). The parent of porphyrin is porphine, a rare chemical com ...

s, which feature 16-membered central rings, form in the absence of metal templates. CurtisMacrocycle

Concept in catalysis

In a general sense, transition metal-based

catalysis Catalysis () is the process of increasing the rate of a chemical reaction by adding a substance known as a catalyst (). Catalysts are not consumed in the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recyc ...

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 In chemistry, homogeneous catalysis is catalysis by a soluble catalyst in a solution. Homogeneous catalysis refers to reactions where the catalyst is in the same phase as the reactants, principally in solution. In contrast, heterogeneous catalysis ...

, the cyclo-oligomerization of acetylene to

cyclooctatetraene 1,3,5,7-Cyclooctatetraene (COT) is an unsaturated derivative of cyclooctane, with the formula C8H8. It is also known as nnulene. This polyunsaturated hydrocarbon is a colorless to light yellow flammable liquid at room temperature. Because of ...

at a

nickel Nickel is a chemical element with symbol Ni and atomic number 28. It is a silvery-white lustrous metal with a slight golden tinge. Nickel is a hard and ductile transition metal. Pure nickel is chemically reactive but large pieces are slow to ...

(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 Triphenylphosphine (IUPAC name: triphenylphosphane) is a common organophosphorus compound with the formula P(C6H5)3 and often abbreviated to P Ph3 or Ph3P. It is widely used in the synthesis of organic and organometallic compounds. PPh3 exists a ...

were added to occupy one coordination site, then only three molecules of acetylene could bind, and these come together to form

benzene Benzene is an organic chemical compound with the molecular formula C6H6. The benzene molecule is composed of six carbon atoms joined in a planar ring with one hydrogen atom attached to each. Because it contains only carbon and hydrogen atoms, ...

(see

Reppe chemistry Walter Julius Reppe (29 July 1892 in Göringen – 26 July 1969 in Heidelberg) was a German chemist. He is notable for his contributions to the chemistry of acetylene. Education and career Walter Reppe began his study of the natural sciences Un ...

).{{cite journal , doi = 10.1002/jlac.19485600102 , title = Cyclisierende Polymerisation von Acetylen I Über Cyclooctatetraen , year = 1948 , last1 = Reppe , first1 = Walter , last2 = Schlichting , first2 = Otto , last3 = Klager , first3 = Karl , last4 = Toepel , first4 = Tim , journal = Justus Liebigs Annalen der Chemie , volume = 560 , pages = 1–92

References

Polymer chemistry Chemical reactions of ethers