Reaction of Dimethyl Acetylenedicarboxylate with WSe92- and W2Se102-: Synthesis and Characterization of the [W(Se2C2(COOCH3)2)3]2- and [W2Se2(Se2C2(COOCH3)2)4]2- Anions

Mohammad A. Ansari, Charles H. Mahler, James A Ibers*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

29 Scopus citations


The reaction of dimethyl acetylenedicarboxylate (DMA) with WSe92- and W2Se102- affords the new soluble anions W(Se2C2-(COOCH3)2)32- and W2Se2(Se2C2(COOCH3)2)42-, respectively. [AsPh4]2[W(Se2C2(COOCH3)2)3]⋅C7H8.y2DMF crystallizes with eight formula units in the monoclinic space group C62h-C2/c in a cell of dimensions a = 23.21 (3) Å, b = 14.77 (2) A, c = 43.33 (5) Å, and β= 94.46 (4)°. Three chelating diselenene ligands provide trigonal-prismatic coordination about the WIV center. [PPh4]2[W2Se2(Se2C2(COOCH3)2)4]⋅2DMF crystallizes with one formula unit in the triclinic space group C1f-PI in a cell of dimensions a = 13.036 (3) A, b = 13.506 (3) A, c = 13.683 (3) A, a = 104.86 (1)°, β = 110.24 (1)°, and γ = 97.60 (1)°. The anion possesses a center of symmetry. The Wv center is in a distorted-octahedral geometry.77Se NMR spectroscopy of W(Se2C2(COOCH3)2)32- shows the expected one resonance at 5 = 839 ppm (relative to Me2Se), while W2Se2(Se2C2(COOCH3)2)42- shows two lines at δ = 1360 (bridging) ppm and δ = 874 (diselenene) ppm. Variable-temperature studies show that the resonance at 874 ppm broadens as the sample is cooled, collapses by -40 °C, and returns as two peaks at δ = 754 and 967 ppm by -90 °C. The resonance at 1360 ppm and that of W(Se2C2(COOCH3)2)32- show no temperature dependence.

Original languageEnglish (US)
Pages (from-to)2669-2674
Number of pages6
JournalInorganic chemistry
Issue number13
StatePublished - Jun 1 1989

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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