As[P(NMe2)3]2+ als simultane AsI- und PI-Quelle: Synthese und Dichtefunktionalrechnungen planar-tetrakoordinierter Arsonium- und Phosphoniumionen

Drieß, Matthias; Ackermann, Holger; Aust, Joachim; Merz, Klaus; Wüllen, Christoph von

doi:10.1002/1521-3757(20020201)114:3<467::aid-ange467>3.0.co;2-6

Cited by 17 publications

(5 citation statements)

References 26 publications

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“…The heavier congeners featuring P atoms with bulky substituents, [R‐PPP‐R] − and [R‐PAsP‐R] − , were investigated by the groups of Lerner, Jutzi, Scheer, and Wright . Related cationic species of the type [As(P(NMe 2 ) 3 ) 2 ] + were studied by Driess et al . A unique example of an asymmetric group 15 allyl analogue, [R‐NPP‐R] − , was investigated by Niecke et al .…”

Section: Methodsmentioning

confidence: 99%

Synthesis of a Molecule with Four Different Adjacent Pnictogens

Hinz

Schulz

Villinger

2016

Chemistry A European J

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The synthesis of a molecule containing four adjacent different pnictogens was attempted by conversion of a Group 15 allyl analogue anion [Mes*NAsPMes*](-) (Mes*=2,4,6-tri-tert-butylphenyl) with antimony(III) chloride. A suitable precursor is Mes*N(H)AsPMes* (1) for which several syntheses were investigated. The anions afforded by deprotonation of Mes*N(H)AsPMes* were found to be labile and, therefore, salts could not be isolated. However, the in situ generated anions could be quenched with SbCl3 , yielding Mes*N(SbCl2 )AsPMes* (4).

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Section: Methodsmentioning

confidence: 99%

Synthesis of a Molecule with Four Different Adjacent Pnictogens

Hinz

Schulz

Villinger

2016

Chemistry A European J

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“…4 Similarly, Dillon and co-workers have recently used SnCl 2 to reduce AsCl 3 in solutions containing various chelating phosphines to produce salts that were identified by their 31 P NMR shifts and, for two compounds, by X-ray crystallography. 5 An analogous approach to the synthesis of As I cations is the reduction of AsCl 3 by an additional equivalent of phosphine, typically P(NMe 2 ) 3 , 6,7 which generates the arsenic analogues of the acyclic P I cation isolated by Schmidpeter and Lochschmidt. 8 A related, but perhaps surprising, approach to As I -containing molecules involves the reaction of AsCl 3 with lithium salts, either LiC(PPh 2 ) 2 -(SiMe 3 ) or LiN(PPh 2 ) 2 , which act as both metathesis and reducing agents to produce cyclic As I compounds.…”

Section: Introductionmentioning

confidence: 99%

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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“…In more recent work, it has been discovered that 2 (R ) Ph) can be isolated as the iodide salt from the redox reaction of PI 3 with bis(diphenylphosphinoethane). 7 Acyclic cations of the types [R 3 PPPR 3 ] + and [R 3 PAsPR 3 ] + are also known 8,9 as are some N-heterocyclic carbene (NHC) analogues. 10 Typically, the 31 P chemical shifts of the central phosphorus atom of cyclic triphosphenium cations fall in the range of δ -210 to -270.…”

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confidence: 99%

Capture of Phosphorus(I) and Arsenic(I) Moieties by a 1,2-Bis(arylimino)acenaphthene (Aryl-BIAN) Ligand. A Case of Intramolecular Charge Transfer

et al. 2006

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The reaction of PCl3 with SnCl2 in THF solution, followed by treatment with dpp-BIAN (dpp = 2,6-i-Pr2C6H3), affords the phosphenium complex [(dpp-BIAN)P][SnCl5.THF]. The 31P chemical shift (delta 232.5) and the metrical parameters from a single-crystal X-ray diffraction study indicate that the oxidation state of phosphorus in this compound is +3. A similar conclusion was reached regarding the phosphorus oxidation state in [(dpp-BIAN)P][I3], which was prepared via the reaction of dpp-BIAN with PI3 in CH2Cl2 solution. The arsenium salt [(dpp-BIAN)As][SnCl5.THF] was prepared by treatment of AsCl3 with SnCl2 in THF solution, followed by the addition of dpp-BIAN. The X-ray crystal structure of this salt was determined, and the pattern of bond distances and angles indicates that arsenic is present in the +3 oxidation state.

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As[P(NMe2)3]2+ als simultane AsI- und PI-Quelle: Synthese und Dichtefunktionalrechnungen planar-tetrakoordinierter Arsonium- und Phosphoniumionen

Cited by 17 publications

References 26 publications

Synthesis of a Molecule with Four Different Adjacent Pnictogens

Synthesis of a Molecule with Four Different Adjacent Pnictogens

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

Capture of Phosphorus(I) and Arsenic(I) Moieties by a 1,2-Bis(arylimino)acenaphthene (Aryl-BIAN) Ligand. A Case of Intramolecular Charge Transfer

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