Undecafluorodiarsenate Anion:  Synthesis and Crystal Structure of (MeS)₂CSH⁺As₂F₁₁^-

Abstract

Dimethyltrithiocarbonate reacts with the superacidic systems HF/MF(5) and DF/MF(5) (M = As, Sb) to form (MeS)(2)CSX(+)MF(6)(-) (X = H, D). With an excess of AsF(5) the reaction leads to (MeS)(2)CSX(+)As(2)F(11)(-) (X = H, D). The latter salt crystallizes in the monoclinic space group P2(1)/c (No. 14 with a = 7.687(1) Å, b = 21.327(6) Å, c = 8.704(1) Å, and beta = 91.99(1) degrees ) with four formula units per cell. The undecafluorodiarsenate anion contains an As-F-As bridge with two As-F bonds significantly longer than the nonbridging bonds and an As-F-As angle of 159.1(6) degrees. The Raman, IR, and (1)H, (75)As, (19)F, and (13)C NMR spectra of (MeS)(2)CSX(+)SbF(6)(-) and (MeS)(2)CSX(+)As(2)F(11)(-) (X = H, D) are reported.

ProtonatedO,S-Dimethyl Dithiocarbonate − Synthesis, Spectroscopic Characterization and the Crystal Structure of (CH3O)(CH3S)CSH+SbF6−

“…Dialkylxanthogenic acids are well known in the literature, where the work of Gattow and co-workers in the area of the chalcogenocarbonic acids and sulfur chemistry should be mentioned. [4,5] The same configuration is expected for the cation formed by protonation of dimethyl xanthogenates. [8,9] X-ray investigations of a positively charged OCS 2 skeleton are not known.…”

The Crystal Structures of the Trihalogenphosphonium Salts X3PH+As2F11− (X = Cl, Br)

“…(1) 110.3(2) As(1)ϪF (11) 170.1(5) As(1)ϪF (12) 170.0 (7) As (1)ϪF (15)ϪAs (2) 145.9(4) As(1)ϪF (13) 171.0(6) F (11)ϪAs (1)ϪF (12) 89.8(2) As(1)ϪF (14) 172.9(6) F (13)ϪAs (1)ϪF (14) 174.9(4) As(1)ϪF (15) 183.6(6) As (2)ϪF (21) 168.5(5) Br(1)·····F(13) 306.1(3) As (2)ϪF (22) 168.5 (7) Br(1)·····F(21) 325.1(2) As(2)ϪF(23) 167.8(6) Br(2)·····F(22) 300.8 (7) As (2)ϪF (15) 202.0 (6) [a] Symmetry operation: a ϭ x, y Ϫ 1.5, z.…”

Oxidation of CS2 by AsBr4+: The Unexpected Formation of the Simple CS2Br3+ Carbenium Ion

“…From this reaction yellow crystals were obtained in 38 % yield that proved to be 1 (NMR, IR spectroscopy). This demonstrates that 1 may also be obtained by a reaction according to Equation (5) and one cannot distinguish between routes in Equations (4) and (5).…”

“…Oxygen and sulfur lone pair orbitals show slightly weaker donating strength towards a carbenium center than nitrogen, and least stabilizing are those of the halogens. [2] Some structures of simple carbocations including O and S as a-heteroatoms are known, that is, salts of (MeS) 2 CSH + , [3] C(OH) 3 + , [4] (MeO) 2 COH + , [5] (MeO)(MeS)CSH + , [6] and C(SH) 3 + . [7] However, the available information on carbenium ions with a-halogen atoms is scarce.…”