Selenopyrylium

Selenopyrylium is an aromatic heterocyclic compound consisting of a six member ring with five carbon atoms, and a positively charged selenium atom.[1][2]

Selenopyrylium
Names
Other names
Selenopyranium, Selenopyran-1-ium
Identifiers
3D model (JSmol)
ChemSpider
Properties
C5H5Se+
Molar mass 144.065 g·mol−1
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

Naming and numbering

Formerly it was named selenapyrylium. However this is misleading, as "selena" indicates that selenium substitutes for a carbon atom, but actually selenium is substituted for the oxygen atom in pyrylium.[1] In the Hantzsch-Widman system it is called seleninium. This is the name used by Chemical Abstracts. Replacement nomenclature would call this selenoniabenzene.[1]

Numbering in selenopyrylium starts with 1 on the selenium atom and counts up to 6 counter-clockwise on the carbon atoms. The positions adjacent to the chalcogen, numbered 2 and 6 can also be called α, the next two positions 3 and 5 can be termed "β" and the opposite carbon at position 4 can be called "γ".[1]

Occurrence

Because selenopyrylium is a positively charged cation, it takes the solid form as a salt with non-nucleophillic anions like perchlorate, tetrafluoroborate, fluorosulfate, or hexafluorophosphate.[1]

Formation

Selenopyrylium and derivatives can be made from 1,5-diketones (glutaraldehyde), hydrogen selenide along with HCl as a catalyst in acetic acid solvent. A side product is 2,6-bis-(hydroseleno)selenacyclohexane.[1]

When 5-chloro-2,4-pentadienenitrile derivatives react with sodium hydroselenide, or sodium selenite, and is then treated with perchloric acid, a 2-amino-selenopyrilium perchlorate salt results.[1]

Properties

The positive charge is not confined to the selenium atom, but distributes on the ring in several resonance structures, so that the α and γ positions have some positive charge. A nucleophillic attack targets these carbon atoms.[1]

Selenopyrylium has two prominent absorption bands in the ultraviolet spectrum, band I is at 3000 Å, and band II is at 2670 Å. Band I, also known as 1Lb is from the 1B1←1A1 transition. The wavelength is longer and the band is much stronger than that of benzene. This is a bathochromic shift. The wavelength is longer than in thiopyrylium and pyrylium, but the intensity is weaker, due to selenium being less electronegative. Band II, also called 1La, is stronger and longer than that of benzene, thiopyrylium and pyrylium. Band II is polarized in the direction of Se-γ axis.[1]

The nuclear magnetic resonance spectrum shows a 10.98 ppm shift for H2 and 6, 8.77 for H3 and H5 and 9.03 for H4 (BF4− salt dissolved in CD3CN).[1] Compared to other pyryliums H2,6 is more than that of oxygen or sulfur, H3,5 is between that of oxygen and sulfur, and H4 is very similar to thiopyrylium, but is slightly lower. NMR for 13C has the same trends as for the attached hydrogens.[1]

Solvents include trifluoroacetic acid, methanol, dichloromethane, chloroform and acetonitrile.[1]

Derivatives

Many derivatives of selenopyrylium are known with side chains attached to carbons 2,3 or 6. Examples include 4-(p-dimethylaminophenyl)selenopyridinium, 2,6-diphenylselenopyridinium, 4-methyl-2,6-diphenylselenopyrylium, 2,4,6-triphenylselenopyrylium, 2,6-diphenyl-4-(p-dimethylaminophenyl)selenopyrylium. 2,6-di-tert-butylselenopyrylium.[1]

When the ring is fused with other aromatic rings larger aromatic structures such as selenochromenylium, selenoflavylium, and selenoxanthylium result.[1]

See also

References
  1. Doddi, Giancarlo; Ercolani, Gianfranco (1994). "Thiopyrylium, Selenopyrylium, and Telluropyrylium Salts". Advances in Heterocyclic Chemistry. Advances in Heterocyclic Chemistry. 60: 65–195. doi:10.1016/S0065-2725(08)60182-8. ISBN 9780120207602.
  2. Sugimoto, Toyonari (1981). "Reactions of Pyrylium, Thiopyrylium and Selenopyrylium Salts and Their Application to Synthetic Utility". Journal of Synthetic Organic Chemistry, Japan. 39 (1): 1–13. doi:10.5059/yukigoseikyokaishi.39.1.
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