Methylidynephosphane

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Methylidynephosphane
Methylidynephosphane chemical structure HCP-dimensions-from-MW-IR-2D.png
Methylidynephosphane chemical structure
Space filling model HCP-from-MW-IR-3D-vdW.png
Space filling model
Names
Preferred IUPAC name
Methylidynephosphane
Other names
Phosphaethyne
Hydrogen cyaphide[ citation needed ]
Identifiers
3D model (JSmol)
ChemSpider
PubChem CID
  • InChI=1S/CHP/c1-2/h1H
    Key: DPYPSJGRRFKXBE-UHFFFAOYSA-N
  • C#P
Properties
CHP
Molar mass 43.993 g·mol−1
Conjugate base Cyaphide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

Methylidynephosphane (phosphaethyne) is a chemical compound which was the first phosphaalkyne compound discovered, containing the unusual C≡P carbon-phosphorus triple bond.

Contents

Description

Methylidynephosphane is the phosphorus analogue of hydrogen cyanide, with the nitrile nitrogen replaced by phosphorus. Methylidynephosphane can be synthesised via the reaction of phosphine with carbon, [1] but it is extremely reactive and polymerises readily at temperatures above −120 °C. However, several types of derivatives, with bulky groups, such as tert-butyl or trimethylsilyl, substituted for the hydrogen atom, are much more stable, and are useful reagents for the synthesis of various organophosphorus compounds. [2] The PCO and PCS anions are also known. [3]

History

While the existence of the molecule had been discussed, [4] and early attempts had been made to prepare it, methylidynephosphane was first successfully synthesised in 1961, by T.E. Gier of E. I. duPont de Nemours, Inc. [1] [5] Earlier reports of preparing its sodium salt were reported as unreproducible by this author. Methylidynephosphane may have contributed to an explosion that killed Vera Bogdanovskaia, an early chemist pursuing it, one of the first female chemists in Russia, [6] and perhaps the first to die as a result of her own research. [7] [8]

Related Research Articles

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In chemistry, catenation is the bonding of atoms of the same element into a series, called a chain. A chain or a ring shape may be open if its ends are not bonded to each other, or closed if they are bonded in a ring. The words to catenate and catenation reflect the Latin root catena, "chain".

A hypervalent molecule (the phenomenon is sometimes colloquially known as expanded octet) is a molecule that contains one or more main group elements apparently bearing more than eight electrons in their valence shells. Phosphorus pentachloride (PCl5), sulfur hexafluoride (SF6), chlorine trifluoride (ClF3), the chlorite (ClO
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Adamantane Molecule with three connected cyclohexane rings arranged in the "armchair" configuration

Adamantane is an organic compound with a formula C10H16 or, more descriptively, (CH)4(CH2)6. Adamantane molecules can be described as the fusion of three cyclohexane rings. The molecule is both rigid and virtually stress-free. Adamantane is the most stable isomer of C10H16. The spatial arrangement of carbon atoms in the adamantane molecule is the same as in the diamond crystal. This similarity led to the name adamantane, which is derived from the Greek adamantinos (relating to steel or diamond). It is a white solid with a camphor-like odor. It is the simplest diamondoid.

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Phosphaalkyne

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Thioketone

Thioketones (also known as thiones or thiocarbonyls) are organosulfur compounds related to conventional ketones in which the oxygen has been replaced by a sulfur. Instead of a structure of R2C=O, thioketones have the structure R2C=S, which is reflected by the prefix "thio-" in the name of the functional group. Unhindered alkylthioketones typically tend to form polymers or rings.

Carbenium ion

A carbenium ion is a positive ion with the structure RR′R″C+, that is, a chemical species with a trivalent carbon that bears a +1 formal charge.

[n]Radialenes are alicyclic organic compounds containing n cross-conjugated exocyclic double bonds. The double bonds are commonly alkene groups but those with a carbonyl (C=O) group are also called radialenes. For some members the unsubstituted parent radialenes are elusive but many substituted derivatives are known.

Fenestrane

A fenestrane in organic chemistry is a type of chemical compound with a central quaternary carbon atom which serves as a common vertex for four fused carbocycles. They can be regarded as spiro compounds twice over. Because of their inherent strain and instability, fenestranes are of theoretical interest to chemists. The name—proposed in 1972 by Vlasios Georgian and Martin Saltzman—is derived from the Latin word for window, fenestra. Georgian had intended that "fenestrane" solely referred to [4.4.4.4]fenestrane, whose skeletal structure looks like windows, and Kenneth B. Wiberg called that specific structure "windowpane". The term fenestrane has since become generalized to refer to the whole class of molecules that have various other ring-sizes. Georgian recommended rosettane for the class, based on the structural appearance as a rosette of flowers.

<i>tert</i>-Butylphosphaacetylene Chemical compound

tert-Butylphosphaacetylene is an organophosphorus compound. Abbreviated t-BuCP, it was the first example of an isolable phosphaalkyne. Prior to its synthesis, the double bond rule had suggested that elements of Period 3 and higher were unable to form double or triple bonds with lighter main group elements because of weak orbital overlap. The synthesis of t-BuCP discredited much of the double bond rule and opened new studies into the formation of unsaturated phosphorus compounds.

Hexamethylbenzene chemical compound

Hexamethylbenzene, also known as mellitene, is a hydrocarbon with the molecular formula C12H18 and the condensed structural formula C6(CH3)6. It is an aromatic compound and a derivative of benzene, where benzene's six hydrogen atoms have each been replaced by a methyl group. In 1929 Kathleen Lonsdale reported the crystal structure of hexamethylbenzene, demonstrating that the central ring is hexagonal and flat and thereby ending an ongoing debate about the physical parameters of the benzene system. This was a historically significant result, both for the field of X-ray crystallography and for understanding aromaticity.

Vera Yevstafievna Popova Russian chemist

Vera Yevstafievna Popova, née Vera Bogdanovskaya was a Russian chemist. She was one of the first female chemists in Russia, and the first Russian female author of a chemistry textbook. She "probably became the first woman to die in the cause of chemistry" as a result of an explosion in her laboratory.

Edith Humphrey British chemist

Edith Ellen Humphrey was a British inorganic chemist who carried out pioneering work in co-ordination chemistry at the University of Zurich under Alfred Werner. She is thought to be the first British woman to obtain a doctorate in chemistry.

Mildred May Gostling, also published under her married name Mildred Mills, was an English chemist who completed research in carbohydrate chemistry. She was one of the nineteen signatories on a letter from professional female chemists to the Chemical Society requesting that women be accepted as Fellows to the Society.

Phosphirene Chemical compound

Phosphirene is the organophosphorus compound with the formula C2H2PH. It is a colorless gas of no commercial value. As the simplest cyclic, unsaturated organophosphorus compound, phosphirene is the prototype of a family of related compounds that have attracted attention from researchers.

References

  1. 1 2 Gier TE (1961). "HCP, A Unique Phosphorus Compound". J. Am. Chem. Soc. 83 (7): 1769–1770. doi:10.1021/ja01468a058.
  2. Regitz M (1990). "Phosphaalkynes: new building blocks in synthetic chemistry". Chem. Rev. 90: 191–213. doi:10.1021/cr00099a007.
  3. Hubler K, Schwerdtfeger P. (1999). "Theoretical Studies of NMR Chemical Shifts and Vibrational Frequencies in λ3-Phosphaalkynes P≡C-R". Inorg. Chem. 38: 157–164. doi:10.1021/ic9811291.
  4. H. Albers (1950) Angew. Chemie 62:443-467
  5. Philip P. Power (1999) π-Bonding and the Lone Pair Effect in Multiple Bonds between Heavier Main Group Elements, Chem. Rev. 99(12):3463-3503, esp. 3491, see Archived 2016-10-20 at the Wayback Machine , accessed 2 July 2014.
  6. Ledkovskaia-Astman, Marina; Rosenthal, Charlotte; Zirin, Mary Fleming (1994). Dictionary of Russian Women Writers. Westport, CT: Greenwood Publishing Group. ISBN   978-0-313-26265-4.
  7. Rayner-Canham, Marelene; Rayner-Canham, Geoffrey (2001). Women in Chemistry: Their Changing Roles from Alchemical Times to the Mid-twentieth Century. Philadelphia: Chemical Heritage Foundation. p. 64. ISBN   978-0-941901-27-7.
  8. Ogilvie, Marilyn; Harvey, Joy (16 December 2003). Biographical Dictionary of Women in Science. p. 311. ISBN   1135963436.