Synthesis, Structure, and Spectroscopy of [PPh4]2[(NC)Cu(μ-Se)2M(μ-Se)2Cu(CN)]·CH3CN and [PPh4]2[(NC)Cu(μ-Se)2MSe2] (M = Mo, W)

Robert J. Salm; James A. Ibers

doi:10.1021/ic00097a005

Synthesis, Structure, and Spectroscopy of [PPh₄]₂[(NC)Cu(μ-Se)₂M(μ-Se)₂Cu(CN)]·CH₃CN and [PPh₄]₂[(NC)Cu(μ-Se)₂MSe₂] (M = Mo, W)

Robert J. Salm, James A. Ibers^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

32 Scopus citations

Abstract

[PPh₄]₂[MoSe₄] and [PPh₄]₂[WSe₄] react with 2 equiv of CuCN in CH₃CN to afford [PPh₄]₂[(NC)Cu(μ-Se)₂Mo(μ-Se)₂Cu(CN)]·CH₃CN (1) and [PPh₄]₂[(NC)Cu(μ-Se)₂W(μ-Se)₂Cu(CN)]·CH₃CN (2), respectively. Compounds 1 and 2 are isostructural. Compound 1 crystallizes in the triclinic space group C¹_i-P1 with two formula units in a cell of dimensions a = 13.208(3) Å, b = 14.254(3) Å, c = 14.573(3) Å, α= 72.47(3)°, β = 74.09(3) °, and γ = 79.12(3)° at 113 K. Full anisotropic refinement of the structure on F₀² led to a value of R(F) = 0.028 for those 7546 data having F₀² >2σ(F₀²). The [(NC)Cu(μ-Se)₂Mo(μ-Se)₂Cu(CN)]²⁻ anion of 1 comprises two CuCN fragments ligating the opposite edges of a tetrahedral [MoSe₄]²⁻ moiety; the Cu–Mo–Cu angle is 179.13(2)°;. Compounds 1 and 2 display an IR band at 2250 cm⁻¹, which may be assigned to a CN stretching mode of the CH₃CN solvate. Such a solvate molecule was found in the crystal structure of 1. The ⁷⁷Se NMR spectra show a resonance at 1195 ppm for 1 and 920 ppm for 2. Addition of excess PMe₂Ph to solutions of 1 and 2 results in the formation of [PPh₄]₂[(NC)Cu(μ-Se)₂MoSe₂] (3) and [PPh₄]₂[(NC)Cu(μ-Se)₂WSe₂] (4), respectively. Compounds 3 and 4 are isostructural. Compound 3 crystallizes in the monoclinic space group C⁶_2h-C2/c with four formula units in a cell of dimensions a = 11.254(2) Å, b = 20.153(4) Å, c = 20.191(4) Å, and β = 91.74(3)° at 113 K. Full anisotropic refinement of the structure on F₀² led to a value of R(F) = 0.055 for those 3588 reflections having F₀² > 2σ(F₀²)· The [(NC)Cu(μ-Se)₂MoSe₂]²⁻ anion of 3, which has a crystallographically imposed 2-fold axis, comprises a CuCN fragment ligated across an edge of the tetrahedral [MoSe₄]²⁻ moiety. The ⁷⁷Se NMR spectra show resonances at 1030 and 1820 ppm for compound 3 and at 782 and 1383 ppm for compound 4. The remaining NMR, IR, and electronic spectroscopic data of the four title compounds are also consistent with their solid-state structures.

Original language	English (US)
Pages (from-to)	4216-4220
Number of pages	5
Journal	Inorganic chemistry
Volume	33
Issue number	19
DOIs	https://doi.org/10.1021/ic00097a005
State	Published - Sep 1 1994

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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@article{dc9d85b118b84f36ba44a492c7a92d45,

title = "Synthesis, Structure, and Spectroscopy of [PPh4]2[(NC)Cu(μ-Se)2M(μ-Se)2Cu(CN)]·CH3CN and [PPh4]2[(NC)Cu(μ-Se)2MSe2] (M = Mo, W)",

abstract = "[PPh4]2[MoSe4] and [PPh4]2[WSe4] react with 2 equiv of CuCN in CH3CN to afford [PPh4]2[(NC)Cu(μ-Se)2Mo(μ-Se)2Cu(CN)]·CH3CN (1) and [PPh4]2[(NC)Cu(μ-Se)2W(μ-Se)2Cu(CN)]·CH3CN (2), respectively. Compounds 1 and 2 are isostructural. Compound 1 crystallizes in the triclinic space group C1i-P1 with two formula units in a cell of dimensions a = 13.208(3) {\AA}, b = 14.254(3) {\AA}, c = 14.573(3) {\AA}, α= 72.47(3)°, β = 74.09(3) °, and γ = 79.12(3)° at 113 K. Full anisotropic refinement of the structure on F02 led to a value of R(F) = 0.028 for those 7546 data having F02 >2σ(F02). The [(NC)Cu(μ-Se)2Mo(μ-Se)2Cu(CN)]2− anion of 1 comprises two CuCN fragments ligating the opposite edges of a tetrahedral [MoSe4]2− moiety; the Cu–Mo–Cu angle is 179.13(2)°;. Compounds 1 and 2 display an IR band at 2250 cm−1, which may be assigned to a CN stretching mode of the CH3CN solvate. Such a solvate molecule was found in the crystal structure of 1. The 77Se NMR spectra show a resonance at 1195 ppm for 1 and 920 ppm for 2. Addition of excess PMe2Ph to solutions of 1 and 2 results in the formation of [PPh4]2[(NC)Cu(μ-Se)2MoSe2] (3) and [PPh4]2[(NC)Cu(μ-Se)2WSe2] (4), respectively. Compounds 3 and 4 are isostructural. Compound 3 crystallizes in the monoclinic space group C62h-C2/c with four formula units in a cell of dimensions a = 11.254(2) {\AA}, b = 20.153(4) {\AA}, c = 20.191(4) {\AA}, and β = 91.74(3)° at 113 K. Full anisotropic refinement of the structure on F02 led to a value of R(F) = 0.055 for those 3588 reflections having F02 > 2σ(F02)· The [(NC)Cu(μ-Se)2MoSe2]2− anion of 3, which has a crystallographically imposed 2-fold axis, comprises a CuCN fragment ligated across an edge of the tetrahedral [MoSe4]2− moiety. The 77Se NMR spectra show resonances at 1030 and 1820 ppm for compound 3 and at 782 and 1383 ppm for compound 4. The remaining NMR, IR, and electronic spectroscopic data of the four title compounds are also consistent with their solid-state structures.",

author = "Salm, {Robert J.} and Ibers, {James A.}",

year = "1994",

month = sep,

day = "1",

doi = "10.1021/ic00097a005",

language = "English (US)",

volume = "33",

pages = "4216--4220",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "19",

}

TY - JOUR

T1 - Synthesis, Structure, and Spectroscopy of [PPh4]2[(NC)Cu(μ-Se)2M(μ-Se)2Cu(CN)]·CH3CN and [PPh4]2[(NC)Cu(μ-Se)2MSe2] (M = Mo, W)

AU - Salm, Robert J.

AU - Ibers, James A.

PY - 1994/9/1

Y1 - 1994/9/1

N2 - [PPh4]2[MoSe4] and [PPh4]2[WSe4] react with 2 equiv of CuCN in CH3CN to afford [PPh4]2[(NC)Cu(μ-Se)2Mo(μ-Se)2Cu(CN)]·CH3CN (1) and [PPh4]2[(NC)Cu(μ-Se)2W(μ-Se)2Cu(CN)]·CH3CN (2), respectively. Compounds 1 and 2 are isostructural. Compound 1 crystallizes in the triclinic space group C1i-P1 with two formula units in a cell of dimensions a = 13.208(3) Å, b = 14.254(3) Å, c = 14.573(3) Å, α= 72.47(3)°, β = 74.09(3) °, and γ = 79.12(3)° at 113 K. Full anisotropic refinement of the structure on F02 led to a value of R(F) = 0.028 for those 7546 data having F02 >2σ(F02). The [(NC)Cu(μ-Se)2Mo(μ-Se)2Cu(CN)]2− anion of 1 comprises two CuCN fragments ligating the opposite edges of a tetrahedral [MoSe4]2− moiety; the Cu–Mo–Cu angle is 179.13(2)°;. Compounds 1 and 2 display an IR band at 2250 cm−1, which may be assigned to a CN stretching mode of the CH3CN solvate. Such a solvate molecule was found in the crystal structure of 1. The 77Se NMR spectra show a resonance at 1195 ppm for 1 and 920 ppm for 2. Addition of excess PMe2Ph to solutions of 1 and 2 results in the formation of [PPh4]2[(NC)Cu(μ-Se)2MoSe2] (3) and [PPh4]2[(NC)Cu(μ-Se)2WSe2] (4), respectively. Compounds 3 and 4 are isostructural. Compound 3 crystallizes in the monoclinic space group C62h-C2/c with four formula units in a cell of dimensions a = 11.254(2) Å, b = 20.153(4) Å, c = 20.191(4) Å, and β = 91.74(3)° at 113 K. Full anisotropic refinement of the structure on F02 led to a value of R(F) = 0.055 for those 3588 reflections having F02 > 2σ(F02)· The [(NC)Cu(μ-Se)2MoSe2]2− anion of 3, which has a crystallographically imposed 2-fold axis, comprises a CuCN fragment ligated across an edge of the tetrahedral [MoSe4]2− moiety. The 77Se NMR spectra show resonances at 1030 and 1820 ppm for compound 3 and at 782 and 1383 ppm for compound 4. The remaining NMR, IR, and electronic spectroscopic data of the four title compounds are also consistent with their solid-state structures.

AB - [PPh4]2[MoSe4] and [PPh4]2[WSe4] react with 2 equiv of CuCN in CH3CN to afford [PPh4]2[(NC)Cu(μ-Se)2Mo(μ-Se)2Cu(CN)]·CH3CN (1) and [PPh4]2[(NC)Cu(μ-Se)2W(μ-Se)2Cu(CN)]·CH3CN (2), respectively. Compounds 1 and 2 are isostructural. Compound 1 crystallizes in the triclinic space group C1i-P1 with two formula units in a cell of dimensions a = 13.208(3) Å, b = 14.254(3) Å, c = 14.573(3) Å, α= 72.47(3)°, β = 74.09(3) °, and γ = 79.12(3)° at 113 K. Full anisotropic refinement of the structure on F02 led to a value of R(F) = 0.028 for those 7546 data having F02 >2σ(F02). The [(NC)Cu(μ-Se)2Mo(μ-Se)2Cu(CN)]2− anion of 1 comprises two CuCN fragments ligating the opposite edges of a tetrahedral [MoSe4]2− moiety; the Cu–Mo–Cu angle is 179.13(2)°;. Compounds 1 and 2 display an IR band at 2250 cm−1, which may be assigned to a CN stretching mode of the CH3CN solvate. Such a solvate molecule was found in the crystal structure of 1. The 77Se NMR spectra show a resonance at 1195 ppm for 1 and 920 ppm for 2. Addition of excess PMe2Ph to solutions of 1 and 2 results in the formation of [PPh4]2[(NC)Cu(μ-Se)2MoSe2] (3) and [PPh4]2[(NC)Cu(μ-Se)2WSe2] (4), respectively. Compounds 3 and 4 are isostructural. Compound 3 crystallizes in the monoclinic space group C62h-C2/c with four formula units in a cell of dimensions a = 11.254(2) Å, b = 20.153(4) Å, c = 20.191(4) Å, and β = 91.74(3)° at 113 K. Full anisotropic refinement of the structure on F02 led to a value of R(F) = 0.055 for those 3588 reflections having F02 > 2σ(F02)· The [(NC)Cu(μ-Se)2MoSe2]2− anion of 3, which has a crystallographically imposed 2-fold axis, comprises a CuCN fragment ligated across an edge of the tetrahedral [MoSe4]2− moiety. The 77Se NMR spectra show resonances at 1030 and 1820 ppm for compound 3 and at 782 and 1383 ppm for compound 4. The remaining NMR, IR, and electronic spectroscopic data of the four title compounds are also consistent with their solid-state structures.

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