Four new salts of the P2Se8(2-) anion have been prepared, starting from easily available reagents using different reaction strategies including reaction of the elements, oxidation of P4Se3 with alkalimetal diselenides and elemental selenium, and the use of an ionic liquid as a reaction medium. Multinuclear NMR investigations show the presence of both chair-P2Se8(2-) and twist-P2Se8(2-) in solution, with twist-P2Se8(2-) being the predominant conformer. The interconversion between the two conformers is slow on the NMR time scale. Structural investigations of the new salts by single-crystal X-ray diffraction show that chair-P2Se8(2-) is the conformer mostly found in the solid state. A first structural characterization of twist-P2Se8(2-) is reported. The bonding situation in the P2Se8(2-) anion as well as the relative stability of the chair, twist, and boat conformers was elucidated by quantum chemical calculations.
Trimethylsilylcyanide reacts with superacidic solutions AF/MF 5 (A = H, D; M = As, Sb) to form their corresponding salts [ACNA] + [MF 6 ] À , which are protonated forms of hydrogen cyanide and Me 3 SiF as by-product. The salts have been characterized by vibrational spectroscopy and a single-crystal X-ray structure analysis.[DCND] + [AsF 6 ] À crystallizes in the triclinic space group P-1 with one formula unit in the unit cell. The disordered cations are linked with two strong hydrogen bonds to [SbF 6 ] À anions to form chains. The crystal structure and the vibrational spectra are compared to the quantum-chemically calculated (PBE1PBE/6-311 + +G(3df,3dp)) [HCNH(HF) 2 ] + and [DCND (HF) 2 ] + units which simulate the H···F hydrogen bridges found in the solid state. The vibrational modes of the [DCND] + cation are strongly mixed. For their discussion 13 C and 15 N isotopomers have been prepared by the reaction of KCN isotopomers with the superacidic solution AF/AsF 5 .
We present an unusual discrete P-Te anion, P(4)Te(2)(2-), which is readily obtained by the oxidation of white phosphorus with Te(2)(2-) in N-methyl imidazole at ambient temperature. According to the (31)P and (125)Te NMR spectra, the anion P(4)Te(2)(2-) had a bicyclo[1.1.0]tetraphosphane ("butterfly") structure with the tellurium atoms in the exo positions. The anion was remarkably stable at ambient temperature and disproportionated only slowly with the formation of elemental tellurium. P(4)Te(2)(2-) is the first P-Te anion with a bicyclo[1.1.0]tetraphosphane structure. When Se(2)(2-) or S(2)(2-) was reacted with white phosphorus, the analogous seleno- and thiophosphate anions P(4)Se(2)(2-) and P(4)S(2)(2-) were formed, thus completing the series of phosphorus-chalcogen anions P(4)Ch(2)(2-) (Ch = S, Se, Te). The synthesis of P(4)Te(2)(2-) demonstrated that binary P-Te anions do exist as stable species in solution.
The new phosphorus sulfide P(2)S(7), stabilized as the bis(pyridinium) adduct, was obtained from the reaction of P(4)S(10) and sulfur in pyridine, and could be isolated in the form of colourless block-shaped crystals which were characterized using single crystal X-ray diffraction. Coordination of pyridine is weak (d(P-N) = 187 pm) which is supported also by quantum chemical calculations.
A new rare example of a synthetic route in solution to the hexathiohypodiphosphate anion P2S64− is presented. Starting from P4S3, Li2S, and elemental sulfur in pyridine, this reaction yields yellow block‐shaped crystals of [py2Li]4[P2S6] · 2 py (1). The molecular structure of this hitherto unknown compound was determined by single crystal X‐ray diffraction and reveals a heteronorbornane skeleton within the Li4P2S6 entity.
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