One-Step Preparation of Dimethyl Sulfide Substituted Icosahedral Boranes:  The Crystal and Molecular Structures of 1,7-(SMe₂)₂B₁₂H₁₀, 1,12-(SMe₂)₂B₁₂H₁₀, and [SMe₃][B₁₂H₁₁(SMe₂)]·MeCN

Abstract

1,7-(SMe2)2B12H10, 1,12-(SMe2)2B12H10, and [SMe3][B12H11(SMe2)] were prepared and isolated from the self-condensation reaction of BH3·SMe2 in the absence of a solvent. At 150 °C the reaction yields, primarily, two isomers: 1,7-(SMe2)2B12H10, the major component, and 1,12-(SMe2)2B12H10 the minor component, that are separated by thin layer chromatography. Single-crystal X-ray structure determinations were performed for both isomers, confirming the structures inferred from 1H, 11B, and 11B{1H}-11B{1H} (COSY) NMR spectra. Crystal data for 1,7-(SMe2)2B12H10: trigonal P3221, a = 12.901(10) Å, b = 12.901(10) Å, c = 23.73(2) Å, γ = 120°, Z = 9. Crystal data for 1,12-(SMe2)2B12H10: orthorhombic Pbca, a = 10.101(2) Å, b = 11.220(2) Å, c = 13.464(2) Å, Z = 4. At 60 °C, the self-condensation of BH3·SMe2 is very slow, but yields [SMe3][B12H11(SMe2)] as the major product. Multinuclear and 2-dimensional NMR spectra are in full accord with the structure determined by X-ray methods. Crystal data for [SMe3][B12H11(SMe2)]·MeCN: monoclinic P21, a = 8.904(10) Å, b = 9.08(2) Å, c = 12.39(3)Å, β = 93.82°, Z = 2.

Thermal and Photophysical Properties of Highly Quadrupolar Liquid‐Crystalline Derivatives of the [closo‐B12H12]2− Anion

“…The exocage B−N bond length ranges from 1.549(1) Å in 1B[9]‐ p to 1.554(5) Å in 1B[7]‐ p , which is similar to that of 1.559(3) Å in monopyridinium 11 ‐[Et 4 N] and 2,2′‐bipyridinium derivatives . The B−S bond length of 1.898(1) Å in 2B[1]‐ p is similar to that measured for other dialkylsulfonium derivatives, such as 12 ‐[Me 3 S], and 13 (Figure and Table ).…”

“…The intracage dimensions, such as the B−B distances, are typical for this class of derivatives, including the parent cluster B and three closely related derivatives: 11 ‐[Et 4 N], 12 ‐[Me 3 S], and 13 (Figure and Table ). Analysis of data in Table demonstrates that the cage dimensions are sensitive to the nature of the substituent.…”

Unusual Cationic Tris(Dimethylsulfide)-Substituted closo-Boranes: Preparation and Characterization of [1,7,9-(Me2S)3-B12H9] BF4 and [1,2,10-(Me2S)3-B10H7] BF4

“…These features are also observed in the second independent molecule in the crystal structure of 1, as well as in the structures of all 3 isomers of (SMe 2 ) 2 -B 12 H 10 . 10,12 A 10-vertex analogue of compound 1, 1,10-(Me 2 S) 2 -2-(MeS)-B 10 H 7 , 2, was prepared previously in this laboratory. 28 The reported synthetic route to 2 (using DMSO as solvent/ reactant and passage of HCl gas for 1 h) was based on the earlier work of Knoth, Hertler, and Muetterties who had reported the formation of mixtures of monosubstituted B 10 H 9 [S(CH 3 ) 2 ] − and disubstituted B 10 H 8 [S(CH 3 ) 2 ] 2 isomers under these conditions (with no further substitution observed even upon extended reaction times).…”

“…10,12 This method possesses potential for preparation of isotopically enriched clusters for therapeutic applications and has been shown to produce all three isomers of (Me 2 S) 2 B 12 H 10 , as well as [Me 3 S][B 12 H 11 (SMe 2 )]. Furthermore, it avoids the need to handle the large quantities of potentially hazardous diborane required by an earlier similar approach.…”

Al22Br20⋅12 THF: das erste polyedrische Aluminiumsubhalogenid – ein Schritt auf dem Weg zu einer neuen Aluminiummodifikation?

“…[25] entdeckte neutrale 1,12-(SMe 2 ) 2 B 12 H 10 könnte jedoch als ein durch Thioether donorstabilisiertes binäres Boran interpretiert werden.…”