Synthesis and characterization of the new selenolate ligand -SeC6H3-2,6-Mes2 (Mes = C6H2-2,4,6-Me3) and its two-coordinate zinc and manganese derivatives: Factors affecting bending in two-coordinate metal complexes with aryl-substituted ligands

Jeffrey J. Ellison, Karin Ruhlandt, Håkon H. Hope, Philip P. Power

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Abstract

The synthesis and characterization of a novel sterically demanding selenol HSeC6H3-2,6-MeS2, 1 (Mes = -C6H2-2,4,6-Me3), the corresponding diselenide, 2, and some of its metal derivatives are described. Solvated and unsolvated zinc selenolates were prepared by the treatment of the amide Zn{N(SiMe3)2}2 in hexane with 2 equiv of the bulky selenol, 1. Crystallization from hexane produces monomeric Zn(SeC6H3-2,6-Mes2)2, 3, while crystallization from tetrahydrofuran results in the monomeric adduct Zn(SeC6H3-2,6-Mes2)2(THF), 4. Treatment of Mn{N(SiMe3)2}2 with 2 equiv of 1 and crystallization from methylene chloride yields Mn(SeC6H3-2,6-Mes2)2·2CH 2Cl2, 5·2CH2Cl2. The synthesis and structure determination of [Mn(SeMes*)2THF]2·4PhMe (Mes* = -C6H2-2,4,6-t-Bu3), 6, were also undertaken to compare the steric properties of the -SeC6H3-2,6-Mes2 and -SeMes* ligands. The compounds 1-5 were characterized by IR and 1H NMR spectroscopy, and 1-4 were also characterized by 77Se NMR spectroscopy. The structures of 2-6 were determined by X-ray crystallography. In 3 the zinc has a crystallographically required linear coordination whereas the manganese atom in 5 has a bent geometry with a Se-Mn-Se angle of 119.9(1)°. In contrast, the structure of 6 is dimeric even in the presence of THF donor ligands. Crystal data with Mo Kα (λ = 0.710 69 Å) (2 and 5) or Cu Kα (λ = 1.541 78 Å) (3 and 4) radiation at 130 K: 2, a = 16.144(4) Å, b = 15.122(3) Å, c = 16.155(4) Å, β = 91.86(2)°, monoclinic, Z = 4, space group P21/n, R = 0.056; 3, a = 9.318(2) Å, b = 10.904(4) Å, c = 11.796(4) Å, α = 62.25(2)°, β = 73.76(2)°, γ = 68.92(2)°, triclinic, Z = 2, space group P1, R = 0.059; 4, a = 10.621(3) Å, b = 10.828(3) Å, c = 22.491(6) Å, α = 86.76(2)°, β = 85.20(2)°, γ = 60.57(2)°, triclinic, Z = 2, space group P1, R = 0.073; 5·2CH2Cl2, a = 20.061(5) Å, b = 14.705(5) Å, c = 15.781(5) Å, orthorhombic, Z = 8, space group Pccn, R = 0.063; 6·4PhMe, a = 19.000(8) Å, b = 19.626(6) Å, c = 27.687(7) Å, β = 98.18(5)°, Z = 4, space group P21/n, R = 0.086.

Original languageEnglish (US)
Pages (from-to)49-54
Number of pages6
JournalInorganic Chemistry
Volume34
Issue number1
StatePublished - 1995
Externally publishedYes

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Coordination Complexes
Manganese
Crystallization
manganese
Zinc
zinc
Hexanes
Ligands
Derivatives
ligands
Nuclear magnetic resonance spectroscopy
synthesis
metals
crystallization
Methylene Chloride
X ray crystallography
Amides
Metals
nuclear magnetic resonance
Radiation

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

@article{eb15d343a4924cd4a56cd3f16f996180,
title = "Synthesis and characterization of the new selenolate ligand -SeC6H3-2,6-Mes2 (Mes = C6H2-2,4,6-Me3) and its two-coordinate zinc and manganese derivatives: Factors affecting bending in two-coordinate metal complexes with aryl-substituted ligands",
abstract = "The synthesis and characterization of a novel sterically demanding selenol HSeC6H3-2,6-MeS2, 1 (Mes = -C6H2-2,4,6-Me3), the corresponding diselenide, 2, and some of its metal derivatives are described. Solvated and unsolvated zinc selenolates were prepared by the treatment of the amide Zn{N(SiMe3)2}2 in hexane with 2 equiv of the bulky selenol, 1. Crystallization from hexane produces monomeric Zn(SeC6H3-2,6-Mes2)2, 3, while crystallization from tetrahydrofuran results in the monomeric adduct Zn(SeC6H3-2,6-Mes2)2(THF), 4. Treatment of Mn{N(SiMe3)2}2 with 2 equiv of 1 and crystallization from methylene chloride yields Mn(SeC6H3-2,6-Mes2)2·2CH 2Cl2, 5·2CH2Cl2. The synthesis and structure determination of [Mn(SeMes*)2THF]2·4PhMe (Mes* = -C6H2-2,4,6-t-Bu3), 6, were also undertaken to compare the steric properties of the -SeC6H3-2,6-Mes2 and -SeMes* ligands. The compounds 1-5 were characterized by IR and 1H NMR spectroscopy, and 1-4 were also characterized by 77Se NMR spectroscopy. The structures of 2-6 were determined by X-ray crystallography. In 3 the zinc has a crystallographically required linear coordination whereas the manganese atom in 5 has a bent geometry with a Se-Mn-Se angle of 119.9(1)°. In contrast, the structure of 6 is dimeric even in the presence of THF donor ligands. Crystal data with Mo Kα (λ = 0.710 69 {\AA}) (2 and 5) or Cu Kα (λ = 1.541 78 {\AA}) (3 and 4) radiation at 130 K: 2, a = 16.144(4) {\AA}, b = 15.122(3) {\AA}, c = 16.155(4) {\AA}, β = 91.86(2)°, monoclinic, Z = 4, space group P21/n, R = 0.056; 3, a = 9.318(2) {\AA}, b = 10.904(4) {\AA}, c = 11.796(4) {\AA}, α = 62.25(2)°, β = 73.76(2)°, γ = 68.92(2)°, triclinic, Z = 2, space group P1, R = 0.059; 4, a = 10.621(3) {\AA}, b = 10.828(3) {\AA}, c = 22.491(6) {\AA}, α = 86.76(2)°, β = 85.20(2)°, γ = 60.57(2)°, triclinic, Z = 2, space group P1, R = 0.073; 5·2CH2Cl2, a = 20.061(5) {\AA}, b = 14.705(5) {\AA}, c = 15.781(5) {\AA}, orthorhombic, Z = 8, space group Pccn, R = 0.063; 6·4PhMe, a = 19.000(8) {\AA}, b = 19.626(6) {\AA}, c = 27.687(7) {\AA}, β = 98.18(5)°, Z = 4, space group P21/n, R = 0.086.",
author = "Ellison, {Jeffrey J.} and Karin Ruhlandt and Hope, {H{\aa}kon H.} and Power, {Philip P.}",
year = "1995",
language = "English (US)",
volume = "34",
pages = "49--54",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "1",

}

TY - JOUR

T1 - Synthesis and characterization of the new selenolate ligand -SeC6H3-2,6-Mes2 (Mes = C6H2-2,4,6-Me3) and its two-coordinate zinc and manganese derivatives

T2 - Factors affecting bending in two-coordinate metal complexes with aryl-substituted ligands

AU - Ellison, Jeffrey J.

AU - Ruhlandt, Karin

AU - Hope, Håkon H.

AU - Power, Philip P.

PY - 1995

Y1 - 1995

N2 - The synthesis and characterization of a novel sterically demanding selenol HSeC6H3-2,6-MeS2, 1 (Mes = -C6H2-2,4,6-Me3), the corresponding diselenide, 2, and some of its metal derivatives are described. Solvated and unsolvated zinc selenolates were prepared by the treatment of the amide Zn{N(SiMe3)2}2 in hexane with 2 equiv of the bulky selenol, 1. Crystallization from hexane produces monomeric Zn(SeC6H3-2,6-Mes2)2, 3, while crystallization from tetrahydrofuran results in the monomeric adduct Zn(SeC6H3-2,6-Mes2)2(THF), 4. Treatment of Mn{N(SiMe3)2}2 with 2 equiv of 1 and crystallization from methylene chloride yields Mn(SeC6H3-2,6-Mes2)2·2CH 2Cl2, 5·2CH2Cl2. The synthesis and structure determination of [Mn(SeMes*)2THF]2·4PhMe (Mes* = -C6H2-2,4,6-t-Bu3), 6, were also undertaken to compare the steric properties of the -SeC6H3-2,6-Mes2 and -SeMes* ligands. The compounds 1-5 were characterized by IR and 1H NMR spectroscopy, and 1-4 were also characterized by 77Se NMR spectroscopy. The structures of 2-6 were determined by X-ray crystallography. In 3 the zinc has a crystallographically required linear coordination whereas the manganese atom in 5 has a bent geometry with a Se-Mn-Se angle of 119.9(1)°. In contrast, the structure of 6 is dimeric even in the presence of THF donor ligands. Crystal data with Mo Kα (λ = 0.710 69 Å) (2 and 5) or Cu Kα (λ = 1.541 78 Å) (3 and 4) radiation at 130 K: 2, a = 16.144(4) Å, b = 15.122(3) Å, c = 16.155(4) Å, β = 91.86(2)°, monoclinic, Z = 4, space group P21/n, R = 0.056; 3, a = 9.318(2) Å, b = 10.904(4) Å, c = 11.796(4) Å, α = 62.25(2)°, β = 73.76(2)°, γ = 68.92(2)°, triclinic, Z = 2, space group P1, R = 0.059; 4, a = 10.621(3) Å, b = 10.828(3) Å, c = 22.491(6) Å, α = 86.76(2)°, β = 85.20(2)°, γ = 60.57(2)°, triclinic, Z = 2, space group P1, R = 0.073; 5·2CH2Cl2, a = 20.061(5) Å, b = 14.705(5) Å, c = 15.781(5) Å, orthorhombic, Z = 8, space group Pccn, R = 0.063; 6·4PhMe, a = 19.000(8) Å, b = 19.626(6) Å, c = 27.687(7) Å, β = 98.18(5)°, Z = 4, space group P21/n, R = 0.086.

AB - The synthesis and characterization of a novel sterically demanding selenol HSeC6H3-2,6-MeS2, 1 (Mes = -C6H2-2,4,6-Me3), the corresponding diselenide, 2, and some of its metal derivatives are described. Solvated and unsolvated zinc selenolates were prepared by the treatment of the amide Zn{N(SiMe3)2}2 in hexane with 2 equiv of the bulky selenol, 1. Crystallization from hexane produces monomeric Zn(SeC6H3-2,6-Mes2)2, 3, while crystallization from tetrahydrofuran results in the monomeric adduct Zn(SeC6H3-2,6-Mes2)2(THF), 4. Treatment of Mn{N(SiMe3)2}2 with 2 equiv of 1 and crystallization from methylene chloride yields Mn(SeC6H3-2,6-Mes2)2·2CH 2Cl2, 5·2CH2Cl2. The synthesis and structure determination of [Mn(SeMes*)2THF]2·4PhMe (Mes* = -C6H2-2,4,6-t-Bu3), 6, were also undertaken to compare the steric properties of the -SeC6H3-2,6-Mes2 and -SeMes* ligands. The compounds 1-5 were characterized by IR and 1H NMR spectroscopy, and 1-4 were also characterized by 77Se NMR spectroscopy. The structures of 2-6 were determined by X-ray crystallography. In 3 the zinc has a crystallographically required linear coordination whereas the manganese atom in 5 has a bent geometry with a Se-Mn-Se angle of 119.9(1)°. In contrast, the structure of 6 is dimeric even in the presence of THF donor ligands. Crystal data with Mo Kα (λ = 0.710 69 Å) (2 and 5) or Cu Kα (λ = 1.541 78 Å) (3 and 4) radiation at 130 K: 2, a = 16.144(4) Å, b = 15.122(3) Å, c = 16.155(4) Å, β = 91.86(2)°, monoclinic, Z = 4, space group P21/n, R = 0.056; 3, a = 9.318(2) Å, b = 10.904(4) Å, c = 11.796(4) Å, α = 62.25(2)°, β = 73.76(2)°, γ = 68.92(2)°, triclinic, Z = 2, space group P1, R = 0.059; 4, a = 10.621(3) Å, b = 10.828(3) Å, c = 22.491(6) Å, α = 86.76(2)°, β = 85.20(2)°, γ = 60.57(2)°, triclinic, Z = 2, space group P1, R = 0.073; 5·2CH2Cl2, a = 20.061(5) Å, b = 14.705(5) Å, c = 15.781(5) Å, orthorhombic, Z = 8, space group Pccn, R = 0.063; 6·4PhMe, a = 19.000(8) Å, b = 19.626(6) Å, c = 27.687(7) Å, β = 98.18(5)°, Z = 4, space group P21/n, R = 0.086.

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