Monomeric Selenopalladates and Selenoplatinates

Jonathan M. McConnachie, Mohammad A. Ansari, James A Ibers*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

25 Scopus citations

Abstract

The compounds [NEt4]5[2Pd(Se4)2·1/2Pd(Se5)2], α-[PPh4]2[Pt(Se4)3]·DMF, and β-[PPh4]2[Pt(Se4)3] have been prepared from the reaction of the appropriate metal xanthate with Li2Se and Se in DMF. The [PPh4]2[Pt(Se4)]2] compound was isolated from the reduction of α-[PPh4]2[Pt(Se4)3]·DMF with LiBEt3H in DMF. In [NEt4]5[2Pd(Se4)2·1/2Pd(Se5)2] the two independent [Pd(Se4)2]2− anions have a Pd atom chelated by two Se42− chains in slightly distorted square-planar coordination. In the [Pd(Se5)]2− anion the Pd center is in a square-planar coordination being chelated by two Se52− ligands. Both the α- and β- [Pt(Se4)3]2− anions have an octahedral Pt atom chelated by three Se42− chains. The conformation of the chains around the Pt atom is Δλλδ (or Åδδλ) in the α-anion and Δλδδ (or Λδλλ) in the β-anion. The [Pt(Se4)2]2− anion is similar in geometry to the two [Pd(Se4)2]2− anions. 77Se NMR resonances for these ions (δ, ppm): [Pd(Se4)2]2−, 758, 893; [Pd(Se5)2]2−, 509, 647, 875; [Pt(Se4)3]2−, 680, 790; [Pt(Se4)2]2−, 642, 747. The Pt species exhibit the following 195Pt NMR resonances (δ, ppm): [Pt(Se4)3]2−, −4217; [Pt(Se4)2]2−, −4568. Unit cell data: [NEt4]5[2Pd(Se4)2·1/2Pd(Se5)2], space group [formula omitted] a = 26.965(5) Å, b = 10.543(2) Å, c = 26.580(5) Å, β = 106.62(3)*, V = 7241 (2) Å3, Z = 4(−163 °C); α-[PPh4]2[Pt(Se4)3]·DMF, space group [formula omitted], a = 10.066(2) Å, b = 16.383(3) Å, c = 17.253(3) Å, α = 83.08(3)°, β = 86.41(3)°, γ = 86.24(3)°, V = 2814(1) Å3, Z = 2 (−163 °C); β-[PPh4]2[Pt(Se4)3], space group [formula omitted] a = 13.167(3) Å, b = 11.511(2) Å, c = 34.428(7) Å, β = 98.45(3)°, V= 5161(2) Å3, Z = 4 (−163 °C); [PPh4]2[Pt(Se4)2], space group [formula omitted] a = 10.974(2) Å, b = 15.314(3) Å, c = 14.180(3) Å, β = 92.03(3)°, V = 2382(1) Å3, Z = 2 (−163 °C).

Original languageEnglish (US)
Pages (from-to)3250-3255
Number of pages6
JournalInorganic Chemistry
Volume32
Issue number15
DOIs
StatePublished - Jan 1 1993

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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