Synthesis and Characterization of the First Three-Coordinate Donor-Free Magnesium Thiolates, [Mg(STriph)2]2 (Triph = 2,4,6-Ph3C6H2) and [Mg(SMes*26532653)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)21

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Abstract

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*26832683}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 Ka (λ = 0.710 73 Å) at 213 K (for 1 and 3) or CuKa (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 P2,1/n, 1764 (I > 2s(I)) data, R = 0.076; 3, a = 11.083(2) Å, b = 13.325(3) Å, c = 16.466(3) Å, a = 93.58(3)·, P = 95.00(3)·, γ = 106.41(3)·, V = 2314.1(12) Å3, Z = 2, triclinic, space group PI, 6028 (I > 3s(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 P2,1/n, 4118 (I > 2s(I)) data, R = 0.059.

Original languageEnglish (US)
Pages (from-to)3499-3504
Number of pages6
JournalInorganic Chemistry
Volume34
Issue number13
DOIs
StatePublished - Jun 1 1995

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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