Formation of Separated versus Contact Ion Triplets in Magnesium Thiolates. Synthesis and Characterization of [Mg(15-crown-5)(SCPh(3))(2)] and [Mg(15-crown-5)(THF)(2)][S-2,4,6-tBu(3)C(6)H(2))](2).

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 HSCPh(3), resulted in the formation of [Mg(15-crown-5)(SCPh(3))(2)], 1, displaying a seven-coordinate magnesium center with two magnesium-sulfur bonds. Employment of the sterically more encumbered HS-2,4,6-tBu(3)C(6)H(2) yielded a separated cation and anions as displayed in [Mg(15-crown-5)(THF)(2)][S-2,4,6-tBu(3)C(6)H(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 Kalpha (lambda = 0.710 73 Å) are as follows: 1, C(48)H(50)MgO(5)S(2), a = 8.4785(4) Å, b = 9.3595(5) Å, c = 13.8306(6) Å, alpha = 87.332(1) degrees, beta = 85.929(1) degrees, gamma = 68.733(1) degrees, Z = 1, triclinic; 2, C(54)H(94)MgO(7)S(2), a = 13.6755(2) Å, b = 12.8045(6) Å, c = 32.7127(12) Å, beta = 97.87(1) degrees, Z = 4, monoclinic.