Reactions of [M(Se4) 2]2− Anions with TePEt3: 77Se and 125Te Spectra of [MTe.,Se8-n]2− (M = Zn, Cd, Hg; n = 0–4) and Preparation and Crystal Structure of [PPh4]2[Hg(Te2Se2) 2]

John C. Bollinger, James A Ibers*

*Corresponding author for this work

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23 Scopus citations

Abstract

TePEt3 reacts quantitatively with [M(Se4) 2]2− anions (M = Zn, Cd, Hg) in DMF. The ring-bound Se atoms are substituted by Te atoms in the MSe4 rings before the metal-bound Se atoms are. For n = 4, the reaction of n equiv of TePEt3 with 1 equiv of [M(Se4) 2]2− thus affords mixtures of [MTenSe8-n]2− anions, in which the Se atoms remain metal-bound. The pure isomer [PPh4]2[Hg(Te2Se2) 2] crystallizes in the tetragonal space group S42-I4 with four formula units in a unit cell of dimensions a = 21.174(5) Å, c = 10.976(3) Å, and V = 4921(2) Å3 (T = 108 K). The values of the agreement indices R(F) and Rw(F2) are 0.051 and 0.102, respectively. The [PPh4]+ salts of [Hg(Se4) 2]2− and [Hg(TeSe3) (Se4)]2− cocrystallize in a 0.42:0.58 ratio in the monoclinic space group C2h5-P21/n with eight formula units in a unit cell of dimensions a = 22.911(3) Å, b = 20.161(4) Å, c = 23.685(2) Å,ß= 118.65(1) °, and V = 9601(2) Å3 (T = 108 K). The values of the final agreement indices are 0.078 and 0.153. The [PPh4]+ salts of [Hg(Se4) 2]2−, [Hg(TeSe3) (Se4)]2−, [Hg(TeSe3) 2]2−, and [Hg(Te2Se2) (Se4)]2− cocrystallize in a 0.05:0.39:0.43:0.13 ratio in the monoclinic space group C2h5−P21/c with eight formula units in a unit cell of dimensions a = 22.940(3) Å, b = 20.220(2) Å, c = 23.797(2) Å, ß = 118.50(1) °, and V = 9701(2) Å3 (T = 108 K). The values of the agreement indices are 0.059 and 0.127. From the 77Se and 125Te NMR chemical shifts, which are sufficiently sensitive, it was possible with one exception to distinguish every unique chalcogen atom in every [MTenSe8-n]2− anion from every other one; these resonances are assigned and discussed.

Original languageEnglish (US)
Pages (from-to)1859-1867
Number of pages9
JournalInorganic Chemistry
Volume34
Issue number7
DOIs
StatePublished - Mar 1 1995

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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