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

doi:10.1021/ic00303a008

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

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

^*Corresponding author for this work

Chemistry

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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 language	English (US)
Pages (from-to)	650-654
Number of pages	5
Journal	Inorganic chemistry
Volume	28
Issue number	4
DOIs	https://doi.org/10.1021/ic00303a008
State	Published - Feb 1 1989

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Physical and Theoretical Chemistry
Inorganic Chemistry

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Ansari, M. A., Chau, C. N., Mahler, C. H., & Ibers, J. A. (1989). Mixed-metal Selenides: Synthesis And Characterization of The Ni(se₂)(WSe₄)^2-and M(WSe₄)₂^2-(M = Ni, Pd) Anions. Inorganic chemistry, 28(4), 650-654. https://doi.org/10.1021/ic00303a008

@article{34db3907103c4618b717b427a70314cc,

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

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) {\AA}, b = 17.168 (7){\AA}, c = 19.976 (8) {\AA}, 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) {\AA}, b = 12.410 (3) {\AA}, c = 12.557 (3) {\AA}, 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.",

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

year = "1989",

month = feb,

day = "1",

doi = "10.1021/ic00303a008",

language = "English (US)",

volume = "28",

pages = "650--654",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "4",

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TY - JOUR

T1 - Mixed-metal Selenides

T2 - Synthesis And Characterization of The Ni(se2)(WSe4)2-and M(WSe4)22-(M = Ni, Pd) Anions

AU - Ansari, Mohammad A.

AU - Chau, Chung nin

AU - Mahler, Charles H.

AU - Ibers, James A.

PY - 1989/2/1

Y1 - 1989/2/1

N2 - 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.

AB - 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.

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