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

doi:10.1021/ic00312a033

Reaction of Dimethyl Acetylenedicarboxylate with WSe₉^2- and W₂Se₁₀^2-: 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

Chemistry

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Abstract

The reaction of dimethyl acetylenedicarboxylate (DMA) with WSe₉^2- and W₂Se₁₀^2- affords the new soluble anions W(Se₂C₂-(COOCH₃)₂)₃^2- and W₂Se₂(Se₂C₂(COOCH₃)₂)₄^2-, respectively. [AsPh₄]₂[W(Se₂C₂(COOCH₃)₂)₃]⋅C₇H₈.y₂DMF crystallizes with eight formula units in the monoclinic space group C⁶_2h-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 W^IV center. [PPh₄]₂[W₂Se₂(Se₂C₂(COOCH₃)₂)₄]⋅2DMF crystallizes with one formula unit in the triclinic space group C^1_f-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 W^v center is in a distorted-octahedral geometry.⁷⁷Se NMR spectroscopy of W(Se₂C₂(COOCH₃)₂)₃^2- shows the expected one resonance at 5 = 839 ppm (relative to Me₂Se), while W₂Se₂(Se₂C₂(COOCH₃)₂)₄^2- 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)₃^2- show no temperature dependence.

Original language	English (US)
Pages (from-to)	2669-2674
Number of pages	6
Journal	Inorganic chemistry
Volume	28
Issue number	13
DOIs	https://doi.org/10.1021/ic00312a033
State	Published - Jun 1 1989

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Physical and Theoretical Chemistry
Inorganic Chemistry

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@article{42518b2423f141c7bc8127b31a7b5e8d,

title = "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",

abstract = "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) {\AA}, b = 14.77 (2) A, c = 43.33 (5) {\AA}, 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.",

author = "Ansari, {Mohammad A.} and Mahler, {Charles H.} and Ibers, {James A}",

year = "1989",

month = jun,

day = "1",

doi = "10.1021/ic00312a033",

language = "English (US)",

volume = "28",

pages = "2669--2674",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "13",

}

TY - JOUR

T1 - Reaction of Dimethyl Acetylenedicarboxylate with WSe92- and W2Se102-

T2 - Synthesis and Characterization of the [W(Se2C2(COOCH3)2)3]2- and [W2Se2(Se2C2(COOCH3)2)4]2- Anions

AU - Ansari, Mohammad A.

AU - Mahler, Charles H.

AU - Ibers, James A

PY - 1989/6/1

Y1 - 1989/6/1

N2 - 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.

AB - 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.

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DO - 10.1021/ic00312a033

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

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ER -

Reaction of Dimethyl Acetylenedicarboxylate with WSe₉^2- and W₂Se₁₀^2-: Synthesis and Characterization of the [W(Se₂C₂(COOCH₃)₂)₃]^2- and [W₂Se₂(Se₂C₂(COOCH₃)₂)₄]2^- Anions

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