Synthesis and characterization of the first three-coordinate donor-free magnesium thiolates, [Mg(STriph)2]2 (Triph = 2,4,6-Ph3C6H2) and [Mg(SMes*)2]2 (Mes* = 2,4,6-t-Bu3C6H2), and the four-coordinate magnesium thiolate Mg(SMes*)2(OEt ...

Research output: Contribution to journalArticle

38 Citations (Scopus)

Abstract

Full title: Synthesis and characterization of the first three-coordinate donor-free magnesium thiolates, [Mg(STriph)2]2 (Triph = 2,4,6-Ph3C6H2) and [Mg(SMes*)2]2 (Mes* = 2,4,6-t-Bu3C6H2), and the four-coordinate magnesium thiolate Mg(SMes*)2(OEt2)2 and selenolate Mg(SeMes*)2(THF)2. The synthesis and structural characterization of the first three-coordinate dimeric magnesium thiolate [Mg(STriph)2]2, 1 (Triph = 2,4,6-Ph3C6H2), and of the four-coordinate etherates Mg{SMes*}2(Et2O)2, 3 (Mes* = 2,4,6-t-Bu3C6H2), and Mg{SeMes*}2(THF)2, 4, are described. We also report the synthesis and characterization of the dimeric, presumably three-coordinate Mg thiolate [Mg(SMes*)2]2, 2. Compound 1 is prepared in the reaction of Mg(n-Bu/s-Bu)2 or [Mg{N(SiMe3)2}2]2 with 2 equiv of the bulky thiol HSTriph in toluene. The compound exhibits distorted trigonal-planar geometry at the metal center. Compound 2 is accessible by a reaction analogous to that described for 1, using HSMes* instead of HSTriph. Although crystallographic data for 2 are not available, the spectroscopic characterization indicates a dimeric species with a distorted trigonal planar environment at Mg. Compound 3 is synthesized by reacting Mg(n-Bu/s-Bu)2 or alternatively [Mg{N(SiMe3)2}2]2 with 2 equiv of the sterically demanding HSMes* in a hexane/diethyl ether mixture. This compound can also be prepared by the reaction of MgBr2 with 2 equiv of the corresponding lithium thiolate in diethyl ether. Mg{SeMes*}2(THF)2 is prepared by a reaction sequence similar to that described for 3, by the addition of 2 equiv of freshly prepared HSeMes* in a mixture of hexane and tetrahydrofuran. The reaction of MgBr2 with 2 equiv of lithium selenolate in THF affords 4 in good yield. All compounds were characterized by 1H NMR and IR spectroscopy, as well as elemental analysis; species 1, 3, and 4 were also examined by X-ray crystallography. Crystal data with Mo Kα (λ = 0.710 73 Å) at 213 K (for 1 and 3) or CuKα (λ = 1.54178 Å) at 130 K for 4 are as follows: 1, a = 12.055(2) Å, b = 18.341(4) Å, c = 16.635(3) Å, β = 98.75(3)°, V = 3635(2) Å3, Z = 2, monoclinic, space group P21/n, 1764 (I > 2σ(I)) data, R = 0.076; 3, a = 11.083(2) Å, b = 13.325(3) Å, c = 16.466(3) Å, α = 93.58(3)°, β = 95.00(3)°, γ = 106.41(3)°, V = 2314.1(12) Å3, Z = 2, triclinic, space group P1, 6028 (I > 3σ(I)) data, R = 0.072; 4, a = 16.956(7) Å, b = 16.425(5) Å, c = 17.915(6) Å, β = 117.30(2)°, V = 4434(2) Å3, Z = 4, monoclinic, space group P21/n, 4118 (I > 2σ(I)) data, R = 0.059.

Original languageEnglish (US)
Pages (from-to)3499-3504
Number of pages6
JournalInorganic Chemistry
Volume34
Issue number13
StatePublished - 1995

Fingerprint

Magnesium
magnesium
Hexanes
synthesis
Lithium
diethyl ether
Ether
lithium
X ray crystallography
Toluene
Sulfhydryl Compounds
Nuclear magnetic resonance spectroscopy
Infrared spectroscopy
tetrahydrofuran
thiols
Metals
crystallography
toluene
Crystals
Geometry

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

@article{106c988c27f04b02b371983fbeb250c6,
title = "Synthesis and characterization of the first three-coordinate donor-free magnesium thiolates, [Mg(STriph)2]2 (Triph = 2,4,6-Ph3C6H2) and [Mg(SMes*)2]2 (Mes* = 2,4,6-t-Bu3C6H2), and the four-coordinate magnesium thiolate Mg(SMes*)2(OEt ...",
abstract = "Full title: Synthesis and characterization of the first three-coordinate donor-free magnesium thiolates, [Mg(STriph)2]2 (Triph = 2,4,6-Ph3C6H2) and [Mg(SMes*)2]2 (Mes* = 2,4,6-t-Bu3C6H2), and the four-coordinate magnesium thiolate Mg(SMes*)2(OEt2)2 and selenolate Mg(SeMes*)2(THF)2. The synthesis and structural characterization of the first three-coordinate dimeric magnesium thiolate [Mg(STriph)2]2, 1 (Triph = 2,4,6-Ph3C6H2), and of the four-coordinate etherates Mg{SMes*}2(Et2O)2, 3 (Mes* = 2,4,6-t-Bu3C6H2), and Mg{SeMes*}2(THF)2, 4, are described. We also report the synthesis and characterization of the dimeric, presumably three-coordinate Mg thiolate [Mg(SMes*)2]2, 2. Compound 1 is prepared in the reaction of Mg(n-Bu/s-Bu)2 or [Mg{N(SiMe3)2}2]2 with 2 equiv of the bulky thiol HSTriph in toluene. The compound exhibits distorted trigonal-planar geometry at the metal center. Compound 2 is accessible by a reaction analogous to that described for 1, using HSMes* instead of HSTriph. Although crystallographic data for 2 are not available, the spectroscopic characterization indicates a dimeric species with a distorted trigonal planar environment at Mg. Compound 3 is synthesized by reacting Mg(n-Bu/s-Bu)2 or alternatively [Mg{N(SiMe3)2}2]2 with 2 equiv of the sterically demanding HSMes* in a hexane/diethyl ether mixture. This compound can also be prepared by the reaction of MgBr2 with 2 equiv of the corresponding lithium thiolate in diethyl ether. Mg{SeMes*}2(THF)2 is prepared by a reaction sequence similar to that described for 3, by the addition of 2 equiv of freshly prepared HSeMes* in a mixture of hexane and tetrahydrofuran. The reaction of MgBr2 with 2 equiv of lithium selenolate in THF affords 4 in good yield. All compounds were characterized by 1H NMR and IR spectroscopy, as well as elemental analysis; species 1, 3, and 4 were also examined by X-ray crystallography. Crystal data with Mo Kα (λ = 0.710 73 {\AA}) at 213 K (for 1 and 3) or CuKα (λ = 1.54178 {\AA}) at 130 K for 4 are as follows: 1, a = 12.055(2) {\AA}, b = 18.341(4) {\AA}, c = 16.635(3) {\AA}, β = 98.75(3)°, V = 3635(2) {\AA}3, Z = 2, monoclinic, space group P21/n, 1764 (I > 2σ(I)) data, R = 0.076; 3, a = 11.083(2) {\AA}, b = 13.325(3) {\AA}, c = 16.466(3) {\AA}, α = 93.58(3)°, β = 95.00(3)°, γ = 106.41(3)°, V = 2314.1(12) {\AA}3, Z = 2, triclinic, space group P1, 6028 (I > 3σ(I)) data, R = 0.072; 4, a = 16.956(7) {\AA}, b = 16.425(5) {\AA}, c = 17.915(6) {\AA}, β = 117.30(2)°, V = 4434(2) {\AA}3, Z = 4, monoclinic, space group P21/n, 4118 (I > 2σ(I)) data, R = 0.059.",
author = "Karin Ruhlandt",
year = "1995",
language = "English (US)",
volume = "34",
pages = "3499--3504",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "13",

}

TY - JOUR

T1 - Synthesis and characterization of the first three-coordinate donor-free magnesium thiolates, [Mg(STriph)2]2 (Triph = 2,4,6-Ph3C6H2) and [Mg(SMes*)2]2 (Mes* = 2,4,6-t-Bu3C6H2), and the four-coordinate magnesium thiolate Mg(SMes*)2(OEt ...

AU - Ruhlandt, Karin

PY - 1995

Y1 - 1995

N2 - Full title: Synthesis and characterization of the first three-coordinate donor-free magnesium thiolates, [Mg(STriph)2]2 (Triph = 2,4,6-Ph3C6H2) and [Mg(SMes*)2]2 (Mes* = 2,4,6-t-Bu3C6H2), and the four-coordinate magnesium thiolate Mg(SMes*)2(OEt2)2 and selenolate Mg(SeMes*)2(THF)2. The synthesis and structural characterization of the first three-coordinate dimeric magnesium thiolate [Mg(STriph)2]2, 1 (Triph = 2,4,6-Ph3C6H2), and of the four-coordinate etherates Mg{SMes*}2(Et2O)2, 3 (Mes* = 2,4,6-t-Bu3C6H2), and Mg{SeMes*}2(THF)2, 4, are described. We also report the synthesis and characterization of the dimeric, presumably three-coordinate Mg thiolate [Mg(SMes*)2]2, 2. Compound 1 is prepared in the reaction of Mg(n-Bu/s-Bu)2 or [Mg{N(SiMe3)2}2]2 with 2 equiv of the bulky thiol HSTriph in toluene. The compound exhibits distorted trigonal-planar geometry at the metal center. Compound 2 is accessible by a reaction analogous to that described for 1, using HSMes* instead of HSTriph. Although crystallographic data for 2 are not available, the spectroscopic characterization indicates a dimeric species with a distorted trigonal planar environment at Mg. Compound 3 is synthesized by reacting Mg(n-Bu/s-Bu)2 or alternatively [Mg{N(SiMe3)2}2]2 with 2 equiv of the sterically demanding HSMes* in a hexane/diethyl ether mixture. This compound can also be prepared by the reaction of MgBr2 with 2 equiv of the corresponding lithium thiolate in diethyl ether. Mg{SeMes*}2(THF)2 is prepared by a reaction sequence similar to that described for 3, by the addition of 2 equiv of freshly prepared HSeMes* in a mixture of hexane and tetrahydrofuran. The reaction of MgBr2 with 2 equiv of lithium selenolate in THF affords 4 in good yield. All compounds were characterized by 1H NMR and IR spectroscopy, as well as elemental analysis; species 1, 3, and 4 were also examined by X-ray crystallography. Crystal data with Mo Kα (λ = 0.710 73 Å) at 213 K (for 1 and 3) or CuKα (λ = 1.54178 Å) at 130 K for 4 are as follows: 1, a = 12.055(2) Å, b = 18.341(4) Å, c = 16.635(3) Å, β = 98.75(3)°, V = 3635(2) Å3, Z = 2, monoclinic, space group P21/n, 1764 (I > 2σ(I)) data, R = 0.076; 3, a = 11.083(2) Å, b = 13.325(3) Å, c = 16.466(3) Å, α = 93.58(3)°, β = 95.00(3)°, γ = 106.41(3)°, V = 2314.1(12) Å3, Z = 2, triclinic, space group P1, 6028 (I > 3σ(I)) data, R = 0.072; 4, a = 16.956(7) Å, b = 16.425(5) Å, c = 17.915(6) Å, β = 117.30(2)°, V = 4434(2) Å3, Z = 4, monoclinic, space group P21/n, 4118 (I > 2σ(I)) data, R = 0.059.

AB - Full title: Synthesis and characterization of the first three-coordinate donor-free magnesium thiolates, [Mg(STriph)2]2 (Triph = 2,4,6-Ph3C6H2) and [Mg(SMes*)2]2 (Mes* = 2,4,6-t-Bu3C6H2), and the four-coordinate magnesium thiolate Mg(SMes*)2(OEt2)2 and selenolate Mg(SeMes*)2(THF)2. The synthesis and structural characterization of the first three-coordinate dimeric magnesium thiolate [Mg(STriph)2]2, 1 (Triph = 2,4,6-Ph3C6H2), and of the four-coordinate etherates Mg{SMes*}2(Et2O)2, 3 (Mes* = 2,4,6-t-Bu3C6H2), and Mg{SeMes*}2(THF)2, 4, are described. We also report the synthesis and characterization of the dimeric, presumably three-coordinate Mg thiolate [Mg(SMes*)2]2, 2. Compound 1 is prepared in the reaction of Mg(n-Bu/s-Bu)2 or [Mg{N(SiMe3)2}2]2 with 2 equiv of the bulky thiol HSTriph in toluene. The compound exhibits distorted trigonal-planar geometry at the metal center. Compound 2 is accessible by a reaction analogous to that described for 1, using HSMes* instead of HSTriph. Although crystallographic data for 2 are not available, the spectroscopic characterization indicates a dimeric species with a distorted trigonal planar environment at Mg. Compound 3 is synthesized by reacting Mg(n-Bu/s-Bu)2 or alternatively [Mg{N(SiMe3)2}2]2 with 2 equiv of the sterically demanding HSMes* in a hexane/diethyl ether mixture. This compound can also be prepared by the reaction of MgBr2 with 2 equiv of the corresponding lithium thiolate in diethyl ether. Mg{SeMes*}2(THF)2 is prepared by a reaction sequence similar to that described for 3, by the addition of 2 equiv of freshly prepared HSeMes* in a mixture of hexane and tetrahydrofuran. The reaction of MgBr2 with 2 equiv of lithium selenolate in THF affords 4 in good yield. All compounds were characterized by 1H NMR and IR spectroscopy, as well as elemental analysis; species 1, 3, and 4 were also examined by X-ray crystallography. Crystal data with Mo Kα (λ = 0.710 73 Å) at 213 K (for 1 and 3) or CuKα (λ = 1.54178 Å) at 130 K for 4 are as follows: 1, a = 12.055(2) Å, b = 18.341(4) Å, c = 16.635(3) Å, β = 98.75(3)°, V = 3635(2) Å3, Z = 2, monoclinic, space group P21/n, 1764 (I > 2σ(I)) data, R = 0.076; 3, a = 11.083(2) Å, b = 13.325(3) Å, c = 16.466(3) Å, α = 93.58(3)°, β = 95.00(3)°, γ = 106.41(3)°, V = 2314.1(12) Å3, Z = 2, triclinic, space group P1, 6028 (I > 3σ(I)) data, R = 0.072; 4, a = 16.956(7) Å, b = 16.425(5) Å, c = 17.915(6) Å, β = 117.30(2)°, V = 4434(2) Å3, Z = 4, monoclinic, space group P21/n, 4118 (I > 2σ(I)) data, R = 0.059.

UR - http://www.scopus.com/inward/record.url?scp=0001533957&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0001533957&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0001533957

VL - 34

SP - 3499

EP - 3504

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 13

ER -