ISSN:
0044-2313
Keywords:
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Thiobromo Complexes of Arsenic and Antimony. Preparation and Crystal Structures of (PPh4)2[As2SBr6] · CH2Br2 and (PPh4)2[Sb2SBr6] · CH2Br2(PPh4)2[As2SBr6] · CH2Br2 is formed by the reaction of As2S3, PPh4I and HI in dibromomethane. It can also be obtained, as well as (PPh4)2[Sb2SBr6] · CH2Br2, from (PPh4)2[As2Br8] and (PPh4)3[Sb2Br9], respectively, with bistrimethylsilylsulfide. The crystal structures of the title compounds were determined by X-ray diffraction. They are isotypic with (PPh4)2[As2SCl6] · C2H4Cl2. In the anions [M2SBr6]2- the M atoms (As or Sb) have a distorted octahedral coordination, the two octahedra share acommon face with one bridging S and two Br atoms; the lone electron pairs occupy the trans positions to the S atom. Crystal data: triclinic, space group P1, Z = 2; (PPh4)2[As2SBr6] · CH2Br2, a = 119.1, b = 1203.6, c = 2067.5 pm α= 94.89, β = 97.78, γ = 112.20°, 3046 independent observed reflexions, R = 0.083; (PPh4)2[Sb2SBr6] · CH2Br2, a = 1198.9, b = 1224.3, c = 2085.5pm, α = 95.04, β = 98.48, γ = 112.13°C, 2380 reflexions, R = 0.079.
Notes:
(PPh4)2[As2SBr6] · CH2Br2 entsteht bei der Reaktion von As2S3, PPh4I und HI in Dibrommethan. Es kann, ebenso wie (PPh4)2[Sb2SBr6] · CH2Br2, auch aus (PPh4)2[As2Br8] bzw. (PPh4)3[Sb2Br9] und Bistrimethylsilylsulfid in CH2Br2 erhalten werden. Von den beiden Titelverbindungen wurden die Kristallstrukturen durch Röntgenbeugung bestimmt. Sie sind isotyp zu (PPh4)2[As2SCl6] · C2H4Cl2. In den Anionen [M2SBr6]2- sind die Atome M (= As bzw. Sb) verzerrt oktaedrisch koordiniert, die beiden Oktaeder sind über das S- und zwei Br-Atome flächenverknüpft; die Oktaederspitze in trans-Stellung zum S-Atom wird jeweils vom einsamen Elektronenpaar eingenommen.Kristalldaten: Triklin, Raumgruppe P1, Z = 2; (PPh4)2[As2SBr6]· CH2Br2, a = 1191,1, b = 1203,6 c = 2067,5 pm, α = 94,89, β = 97,78 γ = 112,20°, 3046 unabhängige beobachtete Reflexe, R = 8,3% (PPh4)2[Sb2SBr6]·CH2Br2, a = 1198,9 b = 1224,3, c = 2085,5 pm, α = 95,04, β = 98,48, γ = 112,13°, 2380 Reflexe, R = 7,9%.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/zaac.19885640106
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