Chemical trap

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In chemistry, a chemical trap is a chemical compound that is used to detect unstable compounds. [1] The method relies on efficiency of bimolecular reactions with reagents to produce a more easily characterize trapped product. In some cases, the trapping agent is used in large excess.

Contents

Case studies

Cyclobutadiene

A famous example is the detection of cyclobutadiene released upon oxidation of cyclobutadieneiron tricarbonyl. When this degradation is conducted in the presence of an alkyne, the cyclobutadiene is trapped as a bicyclohexadiene. The requirement for this trapping experiment is that the oxidant (ceric ammonium nitrate) and the trapping agent be mutually compatible. [2]

Cyclobutadiene-DewarbenzeneConversion.png

Diphosphorus

Diphosphorus is an old target of chemists since it is the heavy analogue of N2. Its fleeting existence is inferred by the controlled degradation of certain niobium complexes in the presence of trapping agents. Again, a Diels-Alder strategy is employed in the trapping: [3]

DiphosphorusReaction.png

Silylene

Another classic but elusive family of targets are silylenes, analogues of carbenes. It was proposed that dechlorination of dimethyldichlorosilane generates dimethylsilylene: [4]

SiCl2(CH3)2 + 2 K → Si(CH3)2 + 2 KCl

This inference is supported by conducting the dechlorination in the presence of trimethylsilane, the trapped product being pentamethyldisilane:

Si(CH3)2 + HSi(CH3)3 → (CH3)2Si(H)-Si(CH3)3

Not that the trapping agent does not react with dimethyldichlorosilane or potassium metal.

In some cases, chemical trap is used to detect or infer a compound when present at concentrations below its detection limit or is present in a mixture, where other components interfere with its detection. The trapping agent, for example a dye, reacts with the chemical to be detected, giving a product that is more easily detected.

Related Research Articles

Cyclobutadiene Chemical compound

Cyclobutadiene is an organic compound with the formula C4H4. It is very reactive owing to its tendency to dimerize. Although the parent compound has not been isolated, some substituted derivatives are robust and a single molecule of cyclobutadiene is quite stable. Since the compound degrades by a bimolecular process, the species can be observed by matrix isolation techniques at temperatures below 35 K. It is thought to adopt a rectangular structure.

Antiaromaticity is a characteristic of a cyclic molecule with a π electron system that has higher energy due to the presence of 4n delocalised electrons in it. Unlike aromatic compounds, which follow Hückel's rule and are highly stable, antiaromatic compounds are highly unstable and highly reactive. To avoid the instability of antiaromaticity, molecules may change shape, becoming non-planar and therefore breaking some of the π interactions. In contrast to the diamagnetic ring current present in aromatic compounds, antiaromatic compounds have a paramagnetic ring current, which can be observed by NMR spectroscopy.

Silabenzene Chemical compound

A silabenzene is a heteroaromatic compound containing one or more silicon atoms instead of carbon atoms in benzene. A single substitution gives silabenzene proper; additional substitutions give a disilabenzene, trisilabenzene, etc.

Silylene Chemical compound

Silylene is a chemical compound with the formula SiH2. It is the silicon analog of methylene, the simplest carbene. Silylene is a stable molecule as a gas but rapidly reacts in a bimolecular manner when condensed. Unlike carbenes, which can exist in the singlet or triplet state, silylene (and all of its derivatives) are singlets.

In chemistry, a dehydration reaction is a chemical reaction that involves the loss of water from the reacting molecule or ion. Dehydration reactions are common processes, the reverse of a hydration reaction.

Ozonolysis is an organic reaction where the unsaturated bonds of alkenes, alkynes, or azo compounds are cleaved with ozone. Alkenes and alkynes form organic compounds in which the multiple carbon–carbon bond has been replaced by a carbonyl group while azo compounds form nitrosamines. The outcome of the reaction depends on the type of multiple bond being oxidized and the work-up conditions.

Chlorosilanes are a group of reactive, chlorine-containing chemical compounds, related to silane and used in many chemical processes. Each such chemical has at least one silicon-chlorine bond. Trichlorosilane is produced on the largest scale. The parent chlorosilane is silicon tetrachloride.

Cyclooctatetraene Chemical compound

1,3,5,7-Cyclooctatetraene (COT) is an unsaturated derivative of cyclooctane, with the formula C8H8. It is also known as [8]annulene. This polyunsaturated hydrocarbon is a colorless to light yellow flammable liquid at room temperature. Because of its stoichiometric relationship to benzene, COT has been the subject of much research and some controversy.

Organosilicon compound Organometallic compound containing carbon–silicon bonds

Organosilicon compounds are organometallic compounds containing carbon–silicon bonds. Organosilicon chemistry is the corresponding science of their preparation and properties. Most organosilicon compounds are similar to the ordinary organic compounds, being colourless, flammable, hydrophobic, and stable to air. Silicon carbide is an inorganic compound.

Cyclobutadieneiron tricarbonyl Chemical compound

Cyclobutadieneiron tricarbonyl is an organoiron compound with the formula Fe(C4H4)(CO)3. It is a yellow solid that is soluble in organic solvents. It has been used in organic chemistry as a precursor for cyclobutadiene, which is an elusive species in the free state.

Diphosphorus is an inorganic chemical with the chemical formula P
2
. Unlike nitrogen, its lighter pnictogen neighbor which forms a stable N2 molecule with a nitrogen to nitrogen triple bond, phosphorus prefers a tetrahedral form P4 because P-P pi-bonds are high in energy. Diphosphorus is, therefore, very reactive with a bond-dissociation energy (117 kcal/mol or 490 kJ/mol) half that of dinitrogen. The bond distance has been measured at 1.8934 Å.

Dimethyldichlorosilane is a tetrahedral, organosilicon compound with the formula Si(CH3)2Cl2. At room temperature it is a colorless liquid that readily reacts with water to form both linear and cyclic Si-O chains. Dimethyldichlorosilane is made on an industrial scale as the principal precursor to dimethylsilicone and polysilane compounds.

Sulfene Chemical compound

Sulfene is an extremely reactive chemical compound with the formula H2C=SO2. It is the simplest member of the sulfenes, the group of compounds which are S,S-dioxides of thioaldehydes and thioketones, and have the general formula R2C=SO2.

Organocobalt chemistry Chemistry of compounds with a carbon to cobalt bond

Organocobalt chemistry is the chemistry of organometallic compounds containing a carbon to cobalt chemical bond. Organocobalt compounds are involved in several organic reactions and the important biomolecule vitamin B12 has a cobalt-carbon bond. Many organocobalt compounds exhibit useful catalytic properties, the preeminent example being dicobalt octacarbonyl.

Organoiron chemistry is the chemistry of iron compounds containing a carbon-to-iron chemical bond. Organoiron compounds are relevant in organic synthesis as reagents such as iron pentacarbonyl, diiron nonacarbonyl and disodium tetracarbonylferrate. While iron adopts oxidation states from Fe(−II) through to Fe(VII), Fe(IV) is the highest established oxidation state for organoiron species. Although iron is generally less active in many catalytic applications, it is less expensive and "greener" than other metals. Organoiron compounds feature a wide range of ligands that support the Fe-C bond; as with other organometals, these supporting ligands prominently include phosphines, carbon monoxide, and cyclopentadienyl, but hard ligands such as amines are employed as well.

Organomolybdenum chemistry

Organomolybdenum chemistry is the chemistry of chemical compounds with Mo-C bonds. The heavier group 6 elements molybdenum and tungsten form organometallic compounds similar to those in organochromium chemistry but higher oxidation states tend to be more common.

Tellurol

Tellurols are analogues of alcohols and phenols where tellurium replaces oxygen. Tellurols, selenols, and thiols have similar properties, but tellurols are the least stable. Although they are fundamental representatives of organotellurium compounds, tellurols are lightly studied because of their instability. Tellurol derivatives include telluroesters and tellurocyanates (RTeCN).

Nitrate ester

A nitrate ester is the organic functional group with the formula RONO2, where R stands for any organic residue. They are the esters of nitric acid and alcohols. A well-known example is nitroglycerin, which is not a nitro compound, despite its name.

Christopher "Kit" Colin Cummins is an American chemist currently the Henry Dreyfus Professor at Massachusetts Institute of Technology. He has made contributions to the coordination chemistry of transition metal nitrides, phosphides, and carbides.

Diphosphorus tetrafluoride is a gaseous compound of phosphorus and fluorine with formula P2F4. Two fluorine atoms are connected to each phosphorus atom, and there is a bond between the two phosphorus atoms. Phosphorus can be considered to have oxidation state +2, as indicated by the name phosphorus difluoride.

References

  1. March, Jerry (1985), Advanced Organic Chemistry: Reactions, Mechanisms, and Structure (3rd ed.), New York: Wiley, ISBN   0-471-85472-7
  2. G. F. Emerson, L. Watts, R. Pettit (1965). "Cyclobutadiene- and Benzocyclobutadiene-Iron Tricarbonyl Complexes". J. Am. Chem. Soc. 87: 131–133. doi:10.1021/ja01079a032.{{cite journal}}: CS1 maint: uses authors parameter (link)
  3. Piro, Nicholas A.; Figueroa, Joshua S.; McKellar, Jessica T.; Cumnins, Christopher C. (1 September 2006). "Triple-Bond Reactivity of Diphosphorus Molecules". Science. 313 (5791): 1276–1279. Bibcode:2006Sci...313.1276P. doi:10.1126/science.1129630. PMID   16946068. S2CID   27740669 . Retrieved 21 July 2013.
  4. Skell, P. S.; Goldstein, E. J. (1964). "Dimethylsilene: CH3SiCH3". Journal of the American Chemical Society. 86 (7): 1442–1443. doi:10.1021/ja01061a040.