Formation of separated versus contact ion triplets in magnesium thiolates. Synthesis and cCharacterization of [Mg(15-crown-5)(SCPh3)2] and [Mg(15-crown-5)(THF)2][S-2,4,6-tBu3C6H 2]2

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Abstract

The synthesis and structural characterization of two magnesium thiolate complexes are described. Both compounds were prepared by analogous reactions routes, namely, alkane elimination and transamination, but using differently sized ligands. Utilization of the smaller HSCPh3, resulted in the formation of [Mg(15-crown-5)(SCPh3)2], 1, displaying a seven-coordinate magnesium center with two magnesium-sulfur bonds. Employment of the sterically more encumbered HS-2,4,6-tBu3C6H2 yielded a separated cation and anions as displayed in [Mg(15-crown-5)-(THF)2][S-2,4,6-tBu3C6H 2]2, 2. Compound 2 exhibits a seven-coordinate cation, completing its coordination environment with five metal - crown-ether interactions in addition to two tetrahydrofuran (THF) contacts. The compounds were characterized by IR and NMR spectroscopy in addition to X-ray crystallography. Crystal data with Mo Kα (λ = 0.71073 Å) are as follows: 1, C48H50MgO5S2, a = 8.4785(4) Å, b = 9.3595(5) Å, c = 13.8306(6) Å, a = 87.332(1)°, β= 85.929(1)°, y = 68.733(1)°, Z = 1, triclinic; 2, C54H94MgO7S2, a = 13.6755-(2) Å, b = 12.8045(6) Å, c = 32.7127(12) Å, β= 97.87(1)°, Z = 4, monoclinic.

Original languageEnglish (US)
Pages (from-to)6289-6293
Number of pages5
JournalInorganic Chemistry
Volume38
Issue number26
DOIs
StatePublished - 1999

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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