Manfred Meisel

Synthesis of Phosporus Heterocycles using the Donor-Stabilized Dithiomonometaphosphoryl Chloride as Preparative Tool

The reactivity of the donor-stabilized monometaphosphoryl chloride Py⇒PS2Cl (1) versus multiple bond systems and organometallic compounds has been studied. Thus, on the reaction of 1 with diphenyl acetylene at elevated temperature the five-membered ring systems 2–4 are formed. In the first step probably cycloaddition of the intermediary liberated free monometaphosphoryl chloride PS2Cl with diphenyl acetylene leads to the 1-thia-phosphacyclobut-3-ene 6. This assumption will be supported by theoretical calculations. Attempts to eliminate one sulfur atom from the disulfide bridge in 2 result in the bicyclic ring system 5 besides a compound which is assumed to be 6. The reaction of 1 with tertBuLi gives the dithiaphosphetane 7 whereas with NaN(SiMe3)2 the diazadiphosphetidine 8 is obtained.

Redetermination of Monoclinic VOHPO4.2H2O

Single crystals of monoclinic α-VOHPO4.2H2O, α-oxovanadium(IV) hydrogen phosphate dihydrate, were synthesized by hydrothermal reaction. The structure was refined with good accuracy (R = 0.018) and the results are compared with those of an earlier structure determination from X-ray powder data [Le Bail, Amoros & Beltran-Porter (1989). Eur. J. Solid State Inorg. Chem. 26, 419–426]. Significant differences in bond lengths were found. The structure consists of vanadyl hydrogenphosphate layers running along [100]. The layers are connected via hydrogen bonds.

A NOVEL METHOD FOR THE SYNTHESIS OF POLYCYCLIC PHOSPHORUS CHALCOGENIDES

Abstract With pyridine as activating solvent and depolymerization catalyst and tris(trimethylsilylchalcogeno)phosphane P(ESiMe3)3 (E: S (la), Se (lb)), we succeeded in synthesizing α-[P4E7]M2 (M: [Me3Si-NC5H5]+; E: S (2a), Se (2b)), the first bicycles consisting of phosphorus chalcogen anions with a norbornane skeleton. The constitution of (2a, 2b) was determined by the analysis of their 1H-, 31P- and 77Se-nmr spectra. By variation of the reaction conditions, two P6-suliiir-heterocycles are obtained as the mam products. The31P-nmr spectrum indicates two isomers of P6S7M2 (3a, 4a) with a tricyclic structure related to the hydrocarbon brexan. In addition, the reactions of tBuP(ESiMe3)2 (E: S (5a), Se (5b)) in pyridine are reported.

α,ω-Bis(Dialkylthiophosphoryl)Sulfanes-Products of the Alcoholysis of Sulfur-Rich Phosphorus Sulfides

Abstract The high solubility of sulfur-rich phosphorus sulfides in CS2-especially in the range S:P=2.7 to 4-is the motive for new investigations on this system. DEMARCQ1 suppsed the existence of “molecular products”, but he coulds not prove it by spectroscopic and chemical methods. As we have found the formation of α, ω-bis (fluorodithicphosphoryl) oliqosulfanes at the nucleophilic degradation of phosphorus sulfides with fluorides gives no proof for the existence of oligosulfane bridges in the sulfur-rich phosphorus sulfides. On the reaction of P4S10, elementary sulfur and alka-lifluorides the same products are formed. Sulfur-rich phosphorus sulfides and alcohols also react to mixtures of α,ω-bis (dialkylthiophosphoryl)sulfanes. But these compounds are not obtained by the reaction of P4S10 and sulfur with alcohols.