1,2-Bis(dimethylarsino)benzene

Last updated
1,2-Bis(dimethylarsino)benzene
Diars.png
Diars-3D-balls-A.png
Names
Preferred IUPAC name
(1,2-Phenylene)bis(dimethylarsane)
Identifiers
3D model (JSmol)
AbbreviationsDAS, Diars
2937031
ChEBI
ChemSpider
ECHA InfoCard 100.032.920 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 236-227-9
3780
MeSH 2-Phenylene-bis-dimethylarsine
PubChem CID
UNII
  • InChI=1S/C10H16As2/c1-11(2)9-7-5-6-8-10(9)12(3)4/h5-8H,1-4H3 Yes check.svgY
    Key: HUBWRAMPQVYBRS-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/C10H16As2/c1-11(2)9-7-5-6-8-10(9)12(3)4/h5-8H,1-4H3
    Key: HUBWRAMPQVYBRS-UHFFFAOYAM
  • C[As](C)c1ccccc1[As](C)C
  • C[As](C)C1=CC=CC=C1[As](C)C
Properties
C
10
As
2
H
16
Molar mass 286.0772 g mol−1
AppearanceColourless liquid
Density 1.3992 g cm−3
Boiling point 97 to 101 °C (207 to 214 °F; 370 to 374 K) at 150 Pa
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
Toxic
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 ?)

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." [1]

Contents

Coordination chemistry

Related, but non-chelating organoarsenic ligands include triphenylarsine and trimethylarsine. Work on diars preceded the development of the chelating diphosphine ligands such as dppe, which are now prevalent in homogeneous catalysis.

Diars is a bidentate ligand used in coordination chemistry. It was first described in 1939, [2] but was popularized by R. S. Nyholm for its ability to stabilize metal complexes with unusual oxidation states and coordination numbers, e.g. TiCl4(diars)2. High coordination numbers arise because diars is fairly compact and the As-M bonds are long, which relieves crowding at the metal center. In terms of stabilizing unusual oxidation states, diars stabilizes Ni(III), as in [NiCl2(diars)2]Cl.

Of historical interest is the supposedly diamagnetic [Ni(diars)3](ClO4)2, obtained by heating nickel perchlorate with diars. Octahedral d8 complexes characteristically have triplet ground states, so the diamagnetism of this complex was puzzling. Later by X-ray crystallography, the complex was shown to be pentacoordinate with the formula [Ni(triars)(diars)](ClO4)2, where triars is the tridentate ligand [C6H4As(CH3)2]2As(CH3), arising from the elimination of trimethylarsine. [3] [4]

Preparation and handling

Diars is prepared by the reaction of ortho-dichlorobenzene and sodium dimethylarsenide: [5]

C6H4Cl2 + 2 NaAs(CH3)2 → C6H4(As(CH3)2)2 + 2 NaCl

It is a colorless liquid. Oxygen converts diars to the dioxide, C6H4(As(CH3)2O)2.

Related Research Articles

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

Terpyridine is a heterocyclic compound derived from pyridine. It is a white solid that is soluble in most organic solvents. The compound is mainly used as a ligand in coordination chemistry.

<span class="mw-page-title-main">Metal dithiolene complex</span>

Dithiolene metal complexes are complexes containing 1,2-dithiolene ligands. 1,2-Dithiolene ligands, a particular case of 1,2-dichalcogenolene species along with 1,2-diselenolene derivatives, are unsaturated bidentate ligand wherein the two donor atoms are sulfur. 1,2-Dithiolene metal complexes are often referred to as "metal dithiolenes", "metallodithiolenes" or "dithiolene complexes". Most molybdenum- and tungsten-containing proteins have dithiolene-like moieties at their active sites, which feature the so-called molybdopterin cofactor bound to the Mo or W.

Trimethylarsine (abbreviated TMA or TMAs) is the chemical compound with the formula (CH3)3As, commonly abbreviated AsMe3 or TMAs. This organic derivative of arsine has been used as a source of arsenic in microelectronics industry, 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.

Sir Ronald Sydney Nyholm was an Australian chemist who was a leading figure in inorganic chemistry in the 1950s and 1960s.

<span class="mw-page-title-main">Organonickel chemistry</span> Branch of organometallic chemistry

Organonickel chemistry is a branch of organometallic chemistry that deals with organic compounds featuring nickel-carbon bonds. They are used as a catalyst, as a building block in organic chemistry and in chemical vapor deposition. Organonickel compounds are also short-lived intermediates in organic reactions. The first organonickel compound was nickel tetracarbonyl Ni(CO)4, reported in 1890 and quickly applied in the Mond process for nickel purification. Organonickel complexes are prominent in numerous industrial processes including carbonylations, hydrocyanation, and the Shell higher olefin process.

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.

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

Diphosphines, sometimes called bisphosphanes, are organophosphorus compounds most commonly used as bidentate phosphine ligands in inorganic and organometallic chemistry. They are identified by the presence of two phosphino groups linked by a backbone, and are usually chelating. A wide variety of diphosphines have been synthesized with different linkers and R-groups. Alteration of the linker and R-groups alters the electronic and steric properties of the ligands which can result in different coordination geometries and catalytic behavior in homogeneous catalysts.

<span class="mw-page-title-main">Bis(cyclooctadiene)nickel(0)</span> Chemical compound

Bis(cyclooctadiene)nickel(0) is the organonickel compound with the formula Ni(C8H12)2, also written Ni(cod)2. It is a diamagnetic coordination complex featuring tetrahedral nickel(0) bound to the alkene groups in two 1,5-cyclooctadiene ligands. This highly air-sensitive yellow solid is a common source of Ni(0) in chemical synthesis.

<span class="mw-page-title-main">Benzene-1,2-dithiol</span> Chemical compound

Benzene-1,2-dithiol is the organosulfur compound with the formula C6H4(SH)2. This colourless viscous liquid consists of a benzene ring with a pair of adjacent thiol groups. The conjugate base of this diprotic compound serves as chelating agent in coordination chemistry and a building block for the synthesis of other organosulfur compounds.

<span class="mw-page-title-main">Nickel(II) bis(acetylacetonate)</span> Coordination complex

Nickel(II) bis(acetylacetonate) is a coordination complex with the formula [Ni(acac)2]3, where acac is the anion C5H7O2 derived from deprotonation of acetylacetone. It is a dark green paramagnetic solid that is soluble in organic solvents such as toluene. It reacts with water to give the blue-green diaquo complex Ni(acac)2(H2O)2.

Metal acetylacetonates are coordination complexes derived from the acetylacetonate anion (CH
3
COCHCOCH
3
) and metal ions, usually transition metals. The bidentate ligand acetylacetonate is often abbreviated acac. Typically both oxygen atoms bind to the metal to form a six-membered chelate ring. The simplest complexes have the formula M(acac)3 and M(acac)2. Mixed-ligand complexes, e.g. VO(acac)2, are also numerous. Variations of acetylacetonate have also been developed with myriad substituents in place of methyl (RCOCHCOR). Many such complexes are soluble in organic solvents, in contrast to the related metal halides. Because of these properties, acac complexes are sometimes used as catalyst precursors and reagents. Applications include their use as NMR "shift reagents" and as catalysts for organic synthesis, and precursors to industrial hydroformylation catalysts. C
5
H
7
O
2
in some cases also binds to metals through the central carbon atom; this bonding mode is more common for the third-row transition metals such as platinum(II) and iridium(III).

<span class="mw-page-title-main">Metal-phosphine complex</span>

A metal-phosphine complex is a coordination complex containing one or more phosphine ligands. Almost always, the phosphine is an organophosphine of the type R3P (R = alkyl, aryl). Metal phosphine complexes are useful in homogeneous catalysis. Prominent examples of metal phosphine complexes include Wilkinson's catalyst (Rh(PPh3)3Cl), Grubbs' catalyst, and tetrakis(triphenylphosphine)palladium(0).

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

POCOP is a type of pincer ligand. Pincer type ligands are tridentate ligands that bind three sites on one plane of a metal complex. POCOP forms complexes with one M-C(aryl) bond and two phosphinite ligands. The term POCOP is used both for the ligand, with formula C6H4(OPPh2)2, and its complexes, with formula C6H3(OPPh2)2] (Ph = C6H5)

Nickel compounds are chemical compounds containing the element nickel which is a member of the group 10 of the periodic table. Most compounds in the group have an oxidation state of +2. Nickel is classified as a transition metal with nickel(II) having much chemical behaviour in common with iron(II) and cobalt(II). Many salts of nickel(II) are isomorphous with salts of magnesium due to the ionic radii of the cations being almost the same. Nickel forms many coordination complexes. Nickel tetracarbonyl was the first pure metal carbonyl produced, and is unusual in its volatility. Metalloproteins containing nickel are found in biological systems.

The tetrabromonickelate anion contains a doubly-charged nickel atom (Ni2+) surrounded by four bromide ions in a tetrahedral arrangement. The formula is [NiBr4]2−.

<span class="mw-page-title-main">Transition-metal allyl complex</span>

Transition-metal allyl complexes are coordination complexes with allyl and its derivatives as ligands. Allyl is the radical with the connectivity CH2CHCH2, although as a ligand it is usually viewed as an allyl anion CH2=CH−CH2, which is usually described as two equivalent resonance structures.

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

Salpn is the common name for a chelating ligand, properly called N,N-bis(salicylidene)-1,2-propanediamine, used as a motor oil additive.

<span class="mw-page-title-main">Transition metal pyridine complexes</span>

Transition metal pyridine complexes encompass many coordination complexes that contain pyridine as a ligand. Most examples are mixed-ligand complexes. Many variants of pyridine are also known to coordinate to metal ions, such as the methylpyridines, quinolines, and more complex rings.

<span class="mw-page-title-main">Nickel(II) perchlorate</span> Compound of nickel

Nickel(II) perchlorate is a collection of inorganic compounds with the chemical formula of Ni(ClO4)2(H2O)x. Its colors of these solids vary with the degree of hydration. For example, the hydrate forms cyan crystals, the pentahydrate forms green crystals, but the hexahydrate (Ni(ClO4)2·6H2O) forms blue crystals. Nickel(II) perchlorate hexahydrate is highly soluble in water and soluble in some polar organic solvents.

<span class="mw-page-title-main">Transition metal sulfate complex</span> Coordination complexes with one or more sulfate ligands

Transition metal sulfate complexes or sulfato complexes are coordination complexes with one or more sulfate ligands. Sulfate binds to metals through one, two, three, or all four oxygen atoms. Common are complexes where sulfate is unidentate or chelating bidentate. Examples are respectively [Co(tren)(NH3)(SO4)]+ (tren = tris(2-aminoethyl)amine) and Co(phen)2SO4. All four oxygen atoms of sulfate bond to metals in some Dawson-type polyoxometalates, e.g. [S2Mo18O62]4-.

References

  1. Holleman, A. F.; Wiberg, E. "Inorganic Chemistry" Academic Press: San Diego, 2001. ISBN   0-12-352651-5.
  2. Chatt, J.; Mann, F. G. "The Synthesis of Ditertiary Arsines. Meso- and Racemic Forms of Bis-4-Covalent-Arsenic Compounds" Journal of the Chemical Society, 1939, 610–615. doi : 10.1039/JR9390000610
  3. B. Bosnich, R. S. Nyholm, P. J. Pauling, M. L. Tobe "A nickel(II)-catalyzed synthesis of a triarsine from a diarsine" J. Am. Chem. Soc. 1968, volume 90, pp 4741–4742. doi : 10.1021/ja01019a049
  4. Anthony Nicholl Rail; Some new reactions of a ditertiary arsine ligand; Ph.D. Thesis; University College London; 1973
  5. Feltham, R. D.; Silverthorn, W. "o-Phenylenebis(dimethylarsine)" Inorganic Syntheses 1967, Vol. X, pp. 159–164. doi : 10.1002/9780470132418.ch24