Arsinide

An arsinide, arsanide, dihydridoarsenate(1−) or arsanyl compound is a chemical derivative of arsine, where one hydrogen atom is replaced with a metal or cation. The arsinide ion has formula [AsH2]−. It can be considered as a ligand with name arsenido. Researchers are unenthusiastic about studying arsanyl compounds, because of the toxic chemicals, and their instability.[1] The IUPAC names are arsanide and dihydridoarsenate(1−). For the ligand the name is arsanido. The neutral -AsH2 group is termed arsanyl.

Not to be confused with Arsenide.
Arsinide
Identifiers
ChEBI
ChemSpider
217243
  • InChI=1S/AsH2/h1H2/q-1
    Key: DRQOYSLXOZXEBV-UHFFFAOYSA-N
Properties
AsH2−
Molar mass 76.938 g·mol−1
Related compounds
Related compounds
 arsanylium AsH2+
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

Formation

Alkali metal arsinides can form by bubbling arsine through a liquid ammonia solution of alkali metal such as sodium, potassium or alkaline earth metal such as calcium.[2]


Arsindes are also formed when arsine reacts with thin layers of alkali metals.[3]

The arsine may reduce some compounds to metals, so for example an attempt to make an indium arsinide results in metallic indium.[1]

Reactions

When heated, arsinide compounds lose hydrogen to become an arsenide. NaAsH2 → NaAs + H2[3] With lithium dihydrogen arsenine, it can also lose arsine to become dilithium hydrogen arsine: 2LiAsH2 → Li2AsH + AsH3[3] These reactions take place even at room temperature, and result in a discolouration of the original chemical.[3]

NaAsH2 reacts with alkyl halides to make dialkyl arsine. KAsH2 reacts with an alkyl halide to make trialkyl arsine.[4]

NaAsH2 reacts with diethyl carbonate to yield the 2-arsaethynolate AsCO− ion, (analogous with cyanate) which can be crystallised with the Na ion and 18-crown-6.[5]

Arsinides react with water to yield arsine: KAsH2 + H2O → KOH + AsH3.[6]

Potassium dihydrogen arsenide reacts with halobenzenes (chlorobenzene, bromobenzene, iodobenzene) to produce benzene (C6H6), tetraphenyldiarsine (As(C6H5)2)2 and triphenylarsine (As(C6H5)3).[7]

Potassium dihydrogen arsenide reacts with a silyl halide eg SiH3Cl producing trisilylarsine.[8]

Potassium dihydrogen arsenide reacts with H2As-BH2•NMe3 and a crown ether resulting in [K(C12H24O6)]+[H2As-BH2-AsH2]−.[9]

List
formula system space group unit cell Å volume density comment ref
LiAsH2 [3]
Li2AsH dec at 0° [3]
LiAsH2•2HN3 [3]
LiAsH2•4HN3 [3]
NaAsH2 white; dec at room temperature [2]
Na2AsH [3]
NaAsH2•2HN3 [3]
NaAsH2•4HN3 [3]
LiAl(AsH2)4 [1]
(Dipp2Nacnac)Al(AsH2)2 Dipp2Nacnac=HC[C(Me)N(2,6‐iPr2C6H3)]2 [1]
IDipp⋅AlH2AsH2 IDipp=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) monoclinic I2/a colourless [10]
IDipp⋅AlH(AsH2)2 monoclinic I2/a a 18.3591 b 9.0485 c 34.4864 β 91.580° [10]
KAsH2 stable to 80°C; dec 90° [2]
Ca(AsH2)2 [2]
(Dipp2Nacnac)Ga(AsH2)2 [1]
IDipp⋅GaH2AsH2 monoclinic I2/a colourless [10]
IDipp⋅GaH(AsH2)2 monoclinic I2/a a 18.465 b 9.1493 c 34.661 β 91.509° [10]
Th(TrenTRIPS)AsH2 Th-As 3.065 Å [11]
U(TrenTRIPS)AsH2 U-As 3.004 Å [11]

Arsenic may be substituted by organic or other groups which can then also produce ions, for example potassium methyl arsinide (K+CH3AsH−),[12] or by Si(CH3)3.[1] The doubly bonded ligand =AsH (or AsH2−) is called arsinidene.[11]

References
  1. Li, Bin; Bauer, Susanne; Seidl, Michael; Timoshkin, Alexey Y.; Scheer, Manfred (2019-10-28). "Monomeric β‐Diketiminato Group 13 Metal Dipnictogenide Complexes with Two Terminal EH 2 Groups (E=P, As)". Chemistry – A European Journal. 25 (60): 13714–13718. doi:10.1002/chem.201903887. ISSN 0947-6539. PMC 6899646. PMID 31456252.
  2. Yambushev, Farid Dgamaletdinovich (2019). "Methods for the synthesis of arsines and arsine dihalides". Revista de la Universidad del Zulia (27). ISSN 0041-8811.
  3. Jolly, William L. (March 1959). "The Alkali Metal Salts of Arsine and their Ammoniates. The Reaction of Arsine with Alkali Metals and Alkali Metal Amides". Journal of the American Chemical Society. 81 (5): 1029–1033. doi:10.1021/ja01514a005.
  4. Brandsma, L.; Björlo, O.; Van Der Kerk-Van Hoof, A. C.H.T.M. (January 2000). "Fission of As-As Bonds in Elemental Arsenic by Alkali Metals in Liquid Ammonia. Preparation of Dialkyl and Trialkyl Arsines". Phosphorus, Sulfur, and Silicon and the Related Elements. 164 (1): 83–86. doi:10.1080/10426500008045235. S2CID 98800171.
  5. Hinz, Alexander; Goicoechea, Jose M. (18 July 2016). "The 2-Arsaethynolate Anion: Synthesis and Reactivity Towards Heteroallenes". Angewandte Chemie International Edition. 55 (30): 8536–8541. doi:10.1002/anie.201602310. PMC 5074235. PMID 27093942.
  6. Hummel, S. G.; Zou, Y.; Beyler, C. A.; Grodzinski, P.; Dapkus, P. D.; McManus, J. V.; Zhang, Y.; Skromme, B. J.; Lee, W. I. (23 March 1992). "Characteristics of GaAs, AlGaAs, and InGaAs materials grown by metalorganic chemical vapor deposition using an on‐demand hydride gas generator". Applied Physics Letters. 60 (12): 1483–1485. doi:10.1063/1.107278.
  7. Kuo, Harng-Shen; Jolly, William L. (August 1971). "The reaction of potassium dihydrogen arsenide with halobenzenes". Journal of Organometallic Chemistry. 30 (3): 361–364. doi:10.1016/S0022-328X(00)87519-1.
  8. Jolly, William L.; Norman, Arlan D. (1 August 1967). HYDRIDES OF GROUPS IV AND V.
  9. Kahoun, Tobias (28 September 2020). Synthesis and Coordination Chemistry of Anionic Pnictogenylborane Derivatives (Thesis).
  10. Weinhart, Michael A. K.; Seidl, Michael; Timoshkin, Alexey Y.; Scheer, Manfred (2021-02-15). "NHC‐stabilized Parent Arsanylalanes and ‐gallanes". Angewandte Chemie International Edition. 60 (7): 3806–3811. doi:10.1002/anie.202013849. ISSN 1433-7851. PMC 7898810. PMID 33197127.
  11. Evans, William J.; Hanusa, Timothy P. (2019-01-08). The Heaviest Metals: Science and Technology of the Actinides and Beyond. John Wiley & Sons. p. 114. ISBN 978-1-119-30408-1.
  12. Watt, George W.; Cappel, Norman O. (March 1938). "Liquid ammonia research in 1937—A review". Journal of Chemical Education. 15 (3): 133. doi:10.1021/ed015p133.
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