Octabromocyclohexaarsenate, [As6Br8]2⊖

Müller, Ulrich; Sinning, Heike

doi:10.1002/anie.198901851

Cited by 6 publications

(2 citation statements)

References 11 publications

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“…The dianion is composed of an As 6 I 6 ring arranged in a chair conformation (with each terminal iodine ligand in an equatorial position) and is rendered dianionic by the μ 3 -iodide anions that cap each face of the ring. The metrical parameters for the centrosymmetric dianion, compiled in Table , are essentially identical to those reported for the only other examples of such anions. , For example, the As−As distances range from 2.4599(11) Å to 2.4657(11) Å; the As−I distances to the terminal I atoms range from 2.6367(6) Å to 2.7136(5) Å. The As−I distances to the bridging iodide anions are longer and range from 3.1472(6) Å to 4.1676(5) Å and attest to the distorted arrangement of the heterocubane core.…”

Section: Resultssupporting

confidence: 53%

Stabilized Arsenic(I) Iodide: A Ready Source of Arsenic Iodide Fragments and a Useful Reagent for the Generation of Clusters

Ellis

Macdonald

2004

Inorg. Chem.

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The new stable low oxidation state arsenic(I) iodide reagent [(dppe)As][I] (dppe = 1,2-bis(diphenylphosphino)ethane) exhibits chemistry that is considerably different from its AsIII analogues. While [(dppe)As][I] is not crystalline, the crystal structure of the derivative salt [(dppe)As][(dppe)As2I7] is reported and is compared to that of [(dppe)As]2[SnCl6] x 2CH2Cl2. The air oxidation of [(dppe)As][I] produces crystals of the salt [Ph2P(O)CH2CH2P(OH)Ph2]2[As6I8] x 2CH2Cl2 and suggests that, in contrast to previous studies, the reaction of the univalent arsenic iodide salt with certain oxidants results in the oxidation of the dppe ligand and the release of "AsI-I" fragments that oligomerize to form AsI clusters. Such reactivity is confirmed by the reaction of 6[(dppe)As][I] with 12Me3NO and 2[PPh4][I] to produce [PPh4]2[As6I8] and 6dppeO2. The reactivity is rationalized using density functional theory calculations.

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Section: Resultssupporting

confidence: 53%

Stabilized Arsenic(I) Iodide: A Ready Source of Arsenic Iodide Fragments and a Useful Reagent for the Generation of Clusters

Ellis

Macdonald

2004

Inorg. Chem.

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“…A tentative mechanism of the cation formation involves an attack of the second molecule of i Pr 2 PAcenapLi on 4 or 5 . Only one previous incidence of crystallographic characterisation of octabromohexaarsenate dianion was found in the literature; this was in the form of its tetraphenylphosphonium salt [ 29 ]. The dianion of 6 is essentially isostructural to the previously reported example, both can be seen as an (AsBr) 6 oligoarsine ring in a chair conformation, capped by two bromide anions to form a heterocubane cluster.…”

Section: Resultsmentioning

confidence: 99%

Synthetic and Structural Study of peri-Substituted Phosphine-Arsines

Chalmers

Somisara

Surgenor³

et al. 2021

Molecules

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A series of phosphorus-arsenic peri-substituted acenaphthene species have been isolated and fully characterised, including single crystal X-ray diffraction. Reactions of EBr3 (E = P, As) with iPr2PAcenapLi (Acenap = acenaphthene-5,6-diyl) afforded the thermally stable peri-substitution supported donor–acceptor complexes, iPr2PAcenapEBr23 and 4. Both complexes show a strong P→E dative interaction, as observed by X-ray crystallography and 31P NMR spectroscopy. DFT calculations indicated the unusual As∙∙∙As contact (3.50 Å) observed in the solid state structure of 4 results from dispersion forces rather than metallic interactions. Incorporation of the excess AsBr3 in the crystal structure of 3 promotes the formation of the ion separated species [iPr2PAcenapAsBr]+Br− 5. A decomposition product 6 containing the rare [As6Br8]2– heterocubane dianion was isolated and characterised crystallographically. The reaction between iPr2PAcenapLi and EtAsI2 afforded tertiary arsine (BrAcenap)2AsEt 7, which was subsequently lithiated and reacted with PhPCl2 and Ph2PCl to afford cyclic PhP(Acenap)2AsEt 8 and acyclic EtAs(AcenapPPh2)2 9.

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Arsenic: Inorganic ChemistryBased in part on the article Arsenic: Inorganic Chemistry by Ralph A. Zingaro which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

Muñoz‐Hernández

2005

Encyclopedia of Inorganic Chemistry

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This article reflects the importance and development of the chemistry of inorganic arsenic compounds. Throughout the text the reader will be taken from the chemistry of simple arsenic species found in minerals to such as those arsenic species that reflect the breath of modern inorganic chemistry. Efforts have been made to show developments in fundamental chemistry, materials science, and aspects of arsenic in the environment. Accordingly, Section 2 covers aspects of the preparation of simple arsenic species like the chalcogenides and halogenides. In Section 3 the important arsenic intermetallic and Zintl phases are discussed emphasizing important technological aspects. The chemistry of inorganic arsenic hydrides and halides is presented in Sections 4 and 5 with many important fundamental issues that are difficult to find in one single textbook. Inorganic simple arsenic compounds that bear pnictogen and/or chalcogen atoms are discussed in Sections 6 and 8. In these two sections the chemistry is presented starting from species that are found in minerals to complexes that have arsenic as the central atom introducing exciting discrete arsenic molecules and aspects of supramolecular chemistry. The chemistry of arsenic–carbon species where the carbon atom is strictly inorganic is shown in Section 7. Finally, Section 9 intends to give a brief introduction of the impact of arsenic in the environment, especially focusing on issues related to living organisms.

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Octabromocyclohexaarsenate, [As₆Br₈]^2⊖

Cited by 6 publications

References 11 publications

Stabilized Arsenic(I) Iodide: A Ready Source of Arsenic Iodide Fragments and a Useful Reagent for the Generation of Clusters

Stabilized Arsenic(I) Iodide: A Ready Source of Arsenic Iodide Fragments and a Useful Reagent for the Generation of Clusters

Synthetic and Structural Study of peri-Substituted Phosphine-Arsines

Arsenic: Inorganic ChemistryBased in part on the article Arsenic: Inorganic Chemistry by Ralph A. Zingaro which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

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