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1983 (1)
1Author    Bernt Krebs, Marita Hucke, Michael Hein, Andreas SchäfferRequires cookie*
 Title    Monomere und dimere Oxotrihalogenoselenate(IV): Darstellung, Struktur und Eigenschaften von [As(C6H5)4]SeOCl3 und [N(C2H5)4]SeOCl3 Monomerie and Dimeric Oxotrihalogenoselenates(IV): Preparation, Structure and Properties of [As(C6H5)4]SeOCl3 and [N(C2H5)4] SeOCl3  
 Abstract    The monomeric SeOCl3~ ion, which can be prepared as the tetraphenylarsonium salt from SeOCl2 and As(C6Hs)4C1, was structurally characterized by a low-temperature single crystal X-ray diffraction analysis. [As(C6Hs)4]SeOCl3 is monoclinic, space group P2i/c, with a = 9,332(3), b = 13,761(4), c = 18,985(6) A, ß = 110,97(3)° (at —135 °C), Z = 4; it contains a novel type of y>-trigonal bipyramidal oxotrichloroselenate(IV) anion which is not associated to dimers or polymer chains as in known structures. The equatorial positions are occupied by doubly bonded oxygen (Se-O 1,601(3) Ä) and by one Cl (Se-Cl 2,234(1) A), the axial Se-Cl bonds (2,430(1) and 2,475(1) A) being significantly longer. [N(C2H5)4]SeOCl3, which was obtained as crystals by oxidation of trichloroselenate(II), is triclinic, space group P I, with a = 10,607(3), b = 8,950(2), c = 8,862(2) A, a = 119,79(2)°, ß = 101,07(2)°, y = 96,28(2)°, Z = 2. The X-ray structure analysis shows the anions to be present as centrosymmetric dimers Se202Cl6 2 " like in the [P(CeH5)4] + salt, with two tetragonal SeOCU pyramids linked through a C1---C1 edge and the lone pairs trans to the axial Se-0 bonds (1,589(4) A). Se-Cl bond lengths are 2.270(1) and 2,351(2) A (terminal); 2,698(1) and 2,920(1) A (bridging). The results show that the nature of the reaction products of the Lewis acid SeOCl2 with halogenides as bases changes very sensitively with small variations in cations and environment. The vibrational spectra are discussed. 
  Reference    (Z. Naturforsch. 38b, 20—29 [1983]; eingegangen am 23. September 1982) 
  Published    1983 
  Keywords    Oxohalogenoselenates, Crystal Structure, Selenium, Inert Electron Pair, Selenium Oxychloride 
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 TEI-XML for    default:Reihe_B/38/ZNB-1983-38b-0020.pdf 
 Identifier    ZNB-1983-38b-0020 
 Volume    38