The chlorooxoarsenates(III) (PPh4)(2)[As4O2Cl10]center dot 2CH(3)CN and (PPh4)(2)[As2OCl6]center dot 3CH(3)CN [German]

摘要

(PPh4)(2)[As2Cl8] can be prepared from As2O3, SOCl2 and PPh4Cl in acetonitrile. Its oxidation with chlorine yields PPh4[AsCl6]. This was also obtained directly from arsenic, chlorine and PPh4Cl, (PPh4)(2)[As4O2Cl10] . 2CH(3)CN being a side product; the latter was obtained with high yield from AsCl3, As2O3 and PPh4Cl in acetonitrile. By addition of PPh4Cl it was converted to (PPh4)(2)[As2OCl6] . 3 CH3CN. According to their X-ray crystal structure analyses, both crystallize in the triclinic space group P (1) over bar. The [As4O2Cl10](2-) ion can be regarded as a centrosymmetric association product of two Cl2AsOAsCl2 molecules and two Cl- ions, each Cl- ion being coordinated with all four As atoms. In the [As2OCl6](2-) ion the As atoms are linked via the O atom and two Cl atoms. [References: 18]