Norbert Weferling

Wasserlösliche phosphane: II. Ein neuer syntheseweg für wasserlösliche sekundäre und tertiäre phosphane mit sulfonierten aromatischen resten - kristallstruktur von P(p-C6H4-SO3K)3 · KCl · 0.5H2O

Abstract Water soluble tertiary phosphanes 2, 7, 10–17 with sulfonated aromatic substituents p- C6H4-SO3K and 2,4-C6H3(SO3K)2 can be obtained in good yields by nucleophilic aromatic substitution of fluorine in p-F-C6H4-SO3K (1) or F-C6H3-2,4-(SO3K)2 (5) with PH3 or primary and secondary phosphanes in the superbasic medium dimethyl sulfoxide (DMSO)/KOH(solid). The first water-soluble secondary phosphane HP[C6H3-2,4-(SO3K)2]2 (6) having sulfonated aromatic substituents can be obtained if 5 is reacted under similar conditions with PH3. Highly sulfonated phosphanes (7–9) with remarkable solubilities in water are formed upon reaction of 6 with F-C6H5, nBuBr or C6H5-CH2-Br, respectively, in the superbasic medium. The resulting compounds have been identified by their 1H, 13C(1H and 31P(1H)NMR spectra. X-Ray structural analysis of P(p- C6H4-SO3K)3 · KCl · 0.5H2O shows C3 symmetry for the trianion of 2 with the P CP bond angles (103.5(2)°) and PC bond lengths (1.843(4) A) being almost identical to those in Ph3P.

Preparation and crystal structure determination of a diphosphorus compound with a direct λ5P–λ4P bond

The synthesis of the first example of a λ5P–λ4P diphosphorus compound is described; its structural characterization is based on spectroscopic and single-crystal X-ray diffraction studies.

A rigid double spirocyclic λ5P–O–λ5P oxydiphosphorane with a boat-shaped six-membered ring; X-ray crystal structure

Reaction of the bis(perfluoropinacolyl)bis(trimethylsilyoxy)-phosphorane (4) with thionyl chloride leads to formation of the title compound (5); its structure has been determind by X-ray diffraction.

Formation of Methylphosphonous Acid by Alkylation of Yellow Phosphorus

Methylphosphonous acid is a key intermediate in the synthesis of phosphinic acid salts, a new class of halogen-free flame retardants. This paper describes a novel and simple synthesis of this synthon: By alkylation of elemental yellow phosphorus with methyl chloride under phase-transfer conditions, methylphosphonous acid alkali salt is formed as the main product. Most of the by-products were identified. The mechanism of the reaction is discussed.

Reaktionen koordinierter Liganden, VI [1] Substituenteneinflüsse bei der Bildung von Tri- und Tetraphosphinen in der Koordinationssphäre von Übergangsmetallen / Reactions of Coordinated Ligands, VI [1]. Influence of Substituents on the Formation of Tri- and Tetraphosphines in the Coordination Sphere of Transition Metals

Abstract The lithiumphosphido complex cis-Mo(CO)4(Me2PLi)2 reacts with dichlorophosphines RPCl2(R = Ph, But) to give coordination compounds of tetraphosphines Me2P-PR-PR-PMe2, whereas the complex of the triphosphine cis-Mo(CO)4 (Ph2P-PMe-PPh2) is obtained starting with the lithiumphosphido complex cis-Mo(CO)4(Ph2PLi)2. Phenyldilithiumphosphine and the chlorophosphine complexes cis-Mo(CO)4(R2PCl)2 (R = Me, Ph) give in low yield cis-Mo(CO)4(R2P-PPh-PPh-PR2) and cis-Mo(CO)4(R2P-PPh-PR2). The mechanisms of these reactions are discussed. The {31P}1H- and {1H}31P-NMR spectra are analysed and correlated with the structures of these complexes.

Production of Organophosphorus Compounds from Hydrogen Phosphide

Abstract Technical processes for the production of PH3 and for its radical induced addition to nonactivated olefins are detailed. The influence of the reaction conditions chosen on the selectivity of the PH3/Olefin-reaction is discussed.

Methyldichlorophosphine, a Versatile Starting Material for Flame Retardants and Performance Chemicals

A status report on the chemistry of methyldichlorophosphine derivatives is given with regard to their technical and semi-technical production and application. New applications for oxaphospholane as a flame retardant are shown. The synthesis as well as the flame retardant properties of the aluminium salt of methylethyl-phosphinic acid are described.