Trimethylarsine

Last updated
Trimethylarsine
Structural formula of trimethylarsine with an implicit electron pair Trimethylarsine-2D.png
Structural formula of trimethylarsine with an implicit electron pair
Ball and stick model of trimethylarsine Trimethylarsine-3D-balls.png
Ball and stick model of trimethylarsine
Names
Preferred IUPAC name
Trimethylarsane
Other names
  • Gosio gas
  • Trimethanidoarsenic
Identifiers
3D model (JSmol)
1730780
ChEBI
ChemSpider
ECHA InfoCard 100.008.925 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 209-815-8
141657
MeSH Trimethylarsine
PubChem CID
RTECS number
  • CH8800000
UNII
  • InChI=1S/C3H9As/c1-4(2)3/h1-3H3 Yes check.svgY
    Key: HTDIUWINAKAPER-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/C3H9As/c1-4(2)3/h1-3H3
    Key: HTDIUWINAKAPER-UHFFFAOYAT
  • [As](C)(C)C
  • C[As](C)C
Properties
C3H9As
Molar mass 120.027 g·mol−1
AppearanceColourless liquid
Density 1.124 g cm−3
Melting point −87.3 °C (−125.1 °F; 185.8 K)
Boiling point 56 °C (133 °F; 329 K)
Slightly soluble
Solubility in other solventsorganic solvents
Structure
Trigonal pyramidal
0.86 D
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
Flammable
GHS labelling:
GHS-pictogram-skull.svg GHS-pictogram-pollu.svg
Danger
H301, H331, H410
Flash point −25 °C (−13 °F; 248 K)
Safety data sheet (SDS) External MSDS
Related compounds
Related compounds
Cacodylic acid
Triphenylarsine
Pentamethylarsenic
Trimethylphosphine
Trimethylamine
Supplementary data page
Trimethylarsine (data page)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
X mark.svgN  verify  (what is  Yes check.svgYX mark.svgN ?)

Trimethylarsine (abbreviated TMA or TMAs) is the chemical compound with the formula (CH3)3As, commonly abbreviated AsMe 3 or TMAs. This organic derivative of arsine has been used as a source of arsenic in microelectronics industry, [1] a building block to other organoarsenic compounds, and serves as a ligand in coordination chemistry. It has distinct "garlic"-like smell. Trimethylarsine had been discovered as early as 1854.

Contents

Structure and preparation

AsMe3 is a pyramidal molecule. The As-C distances average 1.519 Å, and the C-As-C angles are 91.83° [2]

Trimethylarsine can be prepared by treatment of arsenic oxide with trimethylaluminium: [3]

As2O3 + 1.5 [AlMe3]2 → 2 AsMe3 + 3/n (MeAl-O)n

Occurrence and reactions

Trimethylarsine is the volatile byproduct of microbial action on inorganic forms of arsenic which are naturally occurring in rocks and soils at the parts-per-million level. [4] Trimethylarsine has been reported only at trace levels (parts per billion) in landfill gas from Germany, Canada, and the U.S.A., and is the major arsenic-containing compound in the gas. [5] [6] [7]

Trimethylarsine is pyrophoric due to the exothermic nature of the following reaction, which initiates combustion:

AsMe3 + 1/2 O2 → OAsMe3 (TMAO)

History

Poisoning events due to a gas produced by certain microbes was assumed to be associated with the arsenic in paint. In 1893 the Italian physician Bartolomeo Gosio published his results on "Gosio gas" that was subsequently shown to contain trimethylarsine. [8] Under wet conditions, the mold Microascus brevicaulis produces significant amounts of methyl arsines via methylation [9] of arsenic-containing inorganic pigments, especially Paris green and Scheele's Green, which were once used in indoor wallpapers. Newer studies show that trimethylarsine has a low toxicity and could therefore not account for the death and the severe health problems observed in the 19th century. [10] [11]

Safety

Trimethylarsine is potentially hazardous, [12] [13] [14] although its toxicity is often overstated. [10]

Related Research Articles

<span class="mw-page-title-main">Arsenic</span> Chemical element, symbol As and atomic number 33

Arsenic is a chemical element; it has symbol As and atomic number 33. It is a metalloid and one of the pnictogens, and therefore shares many properties with its group 15 neighbors phosphorus and antimony. Arsenic is a notoriously toxic heavy metal. It occurs naturally in many minerals, usually in combination with sulfur and metals, but also as a pure elemental crystal. It has various allotropes, but only the grey form, which has a metallic appearance, is important to industry.

<span class="mw-page-title-main">Antimony</span> Chemical element, symbol Sb and atomic number 51

Antimony is a chemical element; it has symbol Sb (from Latin stibium) and atomic number 51. A lustrous grey metal or metalloid, it is found in nature mainly as the sulfide mineral stibnite (Sb2S3). Antimony compounds have been known since ancient times and were powdered for use as medicine and cosmetics, often known by the Arabic name kohl. The earliest known description of the metalloid in the West was written in 1540 by Vannoccio Biringuccio.

In chemistry, the oxidation state, or oxidation number, is the hypothetical charge of an atom if all of its bonds to other atoms were fully ionic. It describes the degree of oxidation of an atom in a chemical compound. Conceptually, the oxidation state may be positive, negative or zero. While fully ionic bonds are not found in nature, many bonds exhibit strong ionicity, making oxidation state a useful predictor of charge.

A metalloid is a type of chemical element which has a preponderance of properties in between, or that are a mixture of, those of metals and nonmetals. There is no standard definition of a metalloid and no complete agreement on which elements are metalloids. Despite the lack of specificity, the term remains in use in the literature of chemistry.

<span class="mw-page-title-main">Nonmetal</span> Chemical element that mostly lacks the characteristics of a metal

Nonmetals are chemical elements that mostly lack distinctive metallic properties. They range from colorless gases like hydrogen to shiny crystals like iodine. Physically, they are usually lighter than metals; brittle or crumbly if solid; and often poor conductors of heat and electricity. Chemically, nonmetals have high electronegativity ; and their oxides tend to be acidic.

<span class="mw-page-title-main">Arsine</span> Chemical compound

Arsine (IUPAC name: arsane) is an inorganic compound with the formula AsH3. This flammable, pyrophoric, and highly toxic pnictogen hydride gas is one of the simplest compounds of arsenic. Despite its lethality, it finds some applications in the semiconductor industry and for the synthesis of organoarsenic compounds. The term arsine is commonly used to describe a class of organoarsenic compounds of the formula AsH3−xRx, where R = aryl or alkyl. For example, As(C6H5)3, called triphenylarsine, is referred to as "an arsine".

<span class="mw-page-title-main">Stibine</span> Chemical compound

Stibine (IUPAC name: stibane) is a chemical compound with the formula SbH3. A pnictogen hydride, this colourless, highly toxic gas is the principal covalent hydride of antimony, and a heavy analogue of ammonia. The molecule is pyramidal with H–Sb–H angles of 91.7° and Sb–H distances of 170.7 pm (1.707 Å). This gas has an offensive smell like hydrogen sulfide (rotten eggs).

<span class="mw-page-title-main">Molybdenum hexacarbonyl</span> Chemical compound

Molybdenum hexacarbonyl (also called molybdenum carbonyl) is the chemical compound with the formula Mo(CO)6. This colorless solid, like its chromium, tungsten, and seaborgium analogues, is noteworthy as a volatile, air-stable derivative of a metal in its zero oxidation state.

<span class="mw-page-title-main">Scheele's Green</span> Highly toxic arsenic-based pigment

Scheele's Green, also called Schloss Green, is chemically a cupric hydrogen arsenite, CuHAsO
3
. It is chemically related to Paris Green. Scheele's Green was invented in 1775 by Carl Wilhelm Scheele. By the end of the 19th century, it had virtually replaced the older green pigments based on copper carbonate. It is a yellowish-green pigment commonly used during the early to mid-19th century in paints as well as being directly incorporated into a variety of products as a colorant. It began to fall out of favor after the 1860s because of its toxicity and the instability of its color in the presence of sulfides and various chemical pollutants. The acutely toxic nature of Scheele's green as well as other arsenic-containing green pigments such as Paris Green may have contributed to the sharp decline in the popularity of the color green in late Victorian society. By the dawn of the 20th century, Scheele's green had completely fallen out of use as a pigment but was still in use as an insecticide into the 1930s. At least two modern reproductions of Scheele's green hue with modern non-toxic pigments have been made, with similar but non-identical color coordinates: one with hex#3c7a18 and another with hex#478800. The latter is the more typically reported color coordinate for Scheele's green.

<span class="mw-page-title-main">Bismuthine</span> Chemical compound of bismuth and hydrogen

Bismuthine (IUPAC name: bismuthane) is the chemical compound with the formula BiH3. As the heaviest analogue of ammonia (a pnictogen hydride), BiH3 is unstable, decomposing to bismuth metal well below 0 °C. This compound adopts the expected pyramidal structure with H–Bi–H angles of around 90°.

<span class="mw-page-title-main">1,2-Bis(dimethylarsino)benzene</span> Chemical compound

1,2-Bis(dimethylarsino)benzene (diars) is the organoarsenic compound with the formula C6H4(As(CH3)2)2. The molecule consists of two dimethylarsino groups attached to adjacent carbon centers of a benzene ring. It is a chelating ligand in coordination chemistry. This colourless oil is commonly abbreviated "diars."

Potassium arsenite (KAsO2) is an inorganic compound that exists in two forms, potassium meta-arsenite (KAsO2) and potassium ortho-arsenite (K3AsO3). It is composed of arsenite ions (AsO33− or AsO2) with arsenic always existing in the +3 oxidation state. Like many other arsenic containing compounds, potassium arsenite is highly toxic and carcinogenic to humans. Potassium arsenite forms the basis of Fowler’s solution, which was historically used as a medicinal tonic, but due to its toxic nature its use was discontinued. Potassium arsenite is still, however, used as a rodenticide.

Organoarsenic chemistry is the chemistry of compounds containing a chemical bond between arsenic and carbon. A few organoarsenic compounds, also called "organoarsenicals," are produced industrially with uses as insecticides, herbicides, and fungicides. In general these applications are declining in step with growing concerns about their impact on the environment and human health. The parent compounds are arsane and arsenic acid. Despite their toxicity, organoarsenic biomolecules are well known.

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<span class="mw-page-title-main">Metallole</span>

Metalloles are metallacycle derivatives of cyclopentadiene in which the carbon atom at position 5, the saturated carbon, is replaced by a heteroatom. In contrast to its parent compound, the numbering of the metallole starts at the heteroatom. Some of these compounds are described as organometallic compounds, but in the list below quite a number of metalloids are present too. Many metalloles are fluorescent. Polymeric derivatives of pyrrole and thiophene are of interest in molecular electronics. Metalloles, which can also be viewed as structural analogs of pyrrole, include:

Arsenic biochemistry refers to biochemical processes that can use arsenic or its compounds, such as arsenate. Arsenic is a moderately abundant element in Earth's crust, and although many arsenic compounds are often considered highly toxic to most life, a wide variety of organoarsenic compounds are produced biologically and various organic and inorganic arsenic compounds are metabolized by numerous organisms. This pattern is general for other related elements, including selenium, which can exhibit both beneficial and deleterious effects. Arsenic biochemistry has become topical since many toxic arsenic compounds are found in some aquifers, potentially affecting many millions of people via biochemical processes.

<span class="mw-page-title-main">Metal bis(trimethylsilyl)amides</span>

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<span class="mw-page-title-main">Bartolomeo Gosio</span>

Bartolomeo Gosio was an Italian medical scientist. He discovered a toxic fume, eponymously named "Gosio gas", which is produced by microorganisms, that killed many people. He identified the chemical nature of the gas as an arsenic compound (arsine), but incorrectly named it as diethylarsine. He also discovered an antibacterial compound called mycophenolic acid from the mould Penicillium brevicompactum. He demonstrated that the novel compound was effective against the deadly anthrax bacterium, Bacillus anthracis. This was the first antibiotic compound isolated in pure and crystallised form. Though the original compound was abandoned in clinical practice due to its adverse effects, its chemical derivative mycophenolate mofetil became the drug of choice as an immunosuppressant in kidney, heart, and liver transplantations.

<span class="mw-page-title-main">Cacodyl cyanide</span> Chemical compound

Cacodyl cyanide is a highly toxic organoarsenic compound discovered by Robert Bunsen in the 1840s. It is very volatile and flammable, as it shares the chemical properties of both arsenic and cyanide.

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References

  1. Hoshino, Masataka (1991). "A mass spectrometric study of the decomposition of trimethylarsine (TMAs) with triethylgallium (TEGa)". Journal of Crystal Growth. 110 (4): 704–712. Bibcode:1991JCrGr.110..704H. doi:10.1016/0022-0248(91)90627-H.
  2. Wells, A.F. (1984). Structural Inorganic Chemistry, fifth edition. Oxford University Press. ISBN   978-0-19-855370-0.
  3. V. V. Gavrilenko, L. A. Chekulaeva, and I. V. Pisareva, "Highly efficient synthesis of trimethylarsine" Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 2122–2123, 1996.
  4. Cullen, W.R., Reimer, K.J. (1989). "Arsenic speciation in the environment". Chem. Rev. 89 (4): 713–764. doi:10.1021/cr00094a002. hdl: 10214/2162 .{{cite journal}}: CS1 maint: multiple names: authors list (link)
  5. Feldmann, J., Cullen, W.R. (1997). "Occurrence of Volatile Transition Metal Compounds in Landfill Gas: Synthesis of Molybdenum and Tungsten Carbonyls in the". Environ. Sci. Technol. 31 (7): 2125–2129. doi:10.1021/es960952y.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  6. Pinel-Raffaitin, P., LeHecho, I., Amouroux, D., Potin-Gautier, M. (2007). "Distribution and Fate of Inorganic and Organic Arsenic Species in Landfill Leachates and Biogases". Environ. Sci. Technol. 41 (13): 4536–4541. Bibcode:2007EnST...41.4536P. doi:10.1021/es0628506. PMID   17695893.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  7. Khoury, J.T.; et al. (April 7, 2008). "Analysis of Volatile Arsenic Compounds in Landfill Gas". Odors & Air Emissions 2008. Phoenix, Arizona: Water Environment Federation.
  8. Frederick Challenger (1955). "Biological methylation". Q. Rev. Chem. Soc. 9 (3): 255–286. doi:10.1039/QR9550900255.
  9. Ronald Bentley & Thomas G. Chasteen (2002). "Microbial Methylation of Metalloids: Arsenic, Antimony, and Bismuth". Microbiology and Molecular Biology Reviews. 66 (2): 250–271. doi:10.1128/MMBR.66.2.250-271.2002. PMC   120786 . PMID   12040126.
  10. 1 2 William R. Cullen; Ronald Bentley (2005). "The toxicity of trimethylarsine: an urban myth". J. Environ. Monit. 7 (1): 11–15. doi:10.1039/b413752n. PMID   15693178.
  11. Frederick Challenger; Constance Higginbottom; Louis Ellis (1933). "The formation of organo-metalloidal compounds by microorganisms. Part I. Trimethylarsine and dimethylethylarsine". J. Chem. Soc.: 95–101. doi:10.1039/JR9330000095.
  12. Andrewes, Paul; et al. (2003). "Dimethylarsine and Trimethylarsine Are Potent Genotoxins In Vitro". Chem. Res. Toxicol. 16 (8): 994–1003. doi:10.1021/tx034063h. PMID   12924927.
  13. Irvin, T.Rick; et al. (1995). "In-vitro Prenatal Toxicity of Trimethylarsine, Trimethylarsine Oxide and Trimethylarsine Sulfide". Applied Organometallic Chemistry. 9 (4): 315–321. doi:10.1002/aoc.590090404.
  14. Hiroshi Yamauchi; Toshikazu Kaise; Keiko Takahashi; Yukio Yamamura (1990). "Toxicity and metabolism of trimethylarsine in mice and hamsters". Fundamental and Applied Toxicology. 14 (2): 399–407. doi:10.1016/0272-0590(90)90219-A. PMID   2318361.