Mixed-metal Selenides: Synthesis And Characterization of The Ni(se2)(WSe4)2-and M(WSe4)22-(M = Ni, Pd) Anions

Mohammad A. Ansari, Chung nin Chau, Charles H. Mahler, James A. Ibers*

*Corresponding author for this work

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Abstract

Reaction of [NH4]2[WSe4] dissolved in DMF with a suspension of Ni(acac)2in DMF in the presence of [PPh4]Cl affords [PPh4]2[Ni(Se2)(WSe4)]. A similar reaction involving NiCl2(PPh3)2in place of Ni(acac)2affords [PPh4]2[Ni(WSe4)2], while the use of PdCl2(C6H5CN)2affords [PPh4]2[Pd(WSe4)2]. The Ni(Se2)(WSe4)2- ion shows77Se NMR resonances at δ 1399, 855, and 608 ppm expected for the structure found in the solid state consisting of a square-planar Ni center bound to a side-on Se2group and to a nearly tetrahedral WSe4group ([PPh4]2[Ni(Se2)(WSe4)], Z = 4, P21/n, a = 14.222 (6) Å, b = 17.168 (7)Å, c = 19.976 (8) Å, β= 110.3 (2)°, R(F2) = 0.076 for 9932 observations). This ion has no known sulfide analogue. The M(WSe4)2 2_ions (M = Ni, Pd) are closely analogous to the known Ni(WS4)2 2_ion and show two77Se NMR resonances (Ni 1628, 994 ppm; Pd 1673, 1135 ppm) consistent with the structure found in the solid state for [PPh4]2[Ni(WSe4)2] in which the square-planar Ni center is bound to two nearly tetrahedral WSe4centers (Z = 1, PI, a = 9.347 (3) Å, b = 12.410 (3) Å, c = 12.557 (3) Å, α = 65.76 (1)°, β = 84.61 (2)°, γ = 69.83 (2)°, R(F2) = 0.090 for 7295 observations). While the Pd(WSe4)2 2-ion is stable in DMF solution at room temperature, the corresponding Ni(WSe4)2 2-ion decomposes to form the Ni(Se2)(WSe4)2-ion.

Original languageEnglish (US)
Pages (from-to)650-654
Number of pages5
JournalInorganic chemistry
Volume28
Issue number4
DOIs
StatePublished - Feb 1 1989

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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