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A mixture of the three isomeric clusters (IV), (Va), and (Vb) is obtained by reacting equimolar quantities of (I), (II), and (III) as shown and separated into (IV) and (V) by fractional crystallization.

Der Komplexbildner (I), der durch Einleiten von Schwefelwasserstoff in eine siedende athanolische Losung von Na-dimethylarsinat dargestellt und als Dihydrat isoliert wurde, setzt sich mit den entsprechenden Metall-Ionen in Wasser-Athanol zu den Komplexen des Typs (II) um, die zum Teil intensiv gefarbt sind.

The complete manuscript of this communication appears in: Angew. Chem. Suppl. 1982, 1962. DOI:10.1002/anie.198219620

Utilisation de la spectrometrie de masse pour l'identification des agregats Mo-S polynucleaires avec de hauts poids moleculaires

Dibenzo(d,f )-1,3,2-dioxaphosphorepines, 2,2′ -Biphenylylenephosphoric Acids, Bis (2,2′ -biphenylylenedithiophosphato) - nickel (II), Gas Chromatography

(-)D-and (+)D-4-methoxyphenylmethyl-thiophosphinic acid, quinine salts of (-)D-and (+)D-4-methoxyphenylmethylthiophosphinic acid, checking of resolution by 31P{ 1H} NMR-spectroscopy (-)D-and(+)D-4-CH3OC6H4(CH3)P(S)OH acid were obtained from fractional crystallization of the quinine salt of the racemic acid. 31P{1H} NMR spectroscopy proved to be very useful in checking the separation process as well as the optical purity of the diastereomers and enan­tiomers.

The mass spectra of several dibenzo (d.f)-1,3,2,-dioxaphosphorepines of the type where X=0, S, Se and R=2,2′-biphenylylene, have been studied. Dibenzochalcogen ions [RX]+˙ stemming directly from [M]+˙ were observed with high intensities, indicating specific migration of X from phosphorus to carbon with simultaneous destruction of the dioxaphosphorepine ring. Simple cleavage of PY as usually observed in similar organophosphorus compounds is not a common process here.

Substitution of the carboxyl group -C(O)OH by -P(O)(OH)2 and -P(O)R(OH) leads to compounds of interest to agriculture, technics and pharmacology. Under these aspects the P-analogon 1 of salicylic acid was prepared, because the monobasic -P(O)H(OH) group resembles more the carboxyl function than the dibasic moiety -P(O)(OH)2.

Starting from tBu2PCl, the title compounds tBu2P(S)NHR′ (R′= Me Et, iPr, tBu) may be easily prepared according to With R′=tBu the amine has to be substituted by its Li-salt [tBuNH]−Li+.

Gas phase ion structures often do not correlate with those of their corresponding neutrals and many ions with unconventional structures have been found to be stable in the gas phase in contrast to their neutral counterparts. Thus, radical ions (a) and (b) are formed under EI-conditions by consecutive elimination of C2H4 from ionized triethylphosphanesulfide Et3P(S). (a) contains tricoordinated phosphorus while the structure of (b) corresponds to an ionized adduct of H2S and the “phosphinidene” Et - P. The structures have been determined on the basis of collisional activation and metastable ion spectra as well as H/D-exchange reactions. Results of semiempirical MO-calculations (MNDO) are reported.

Siliciumtetrachlorid zeigt gegenuber den verschiedenen Atherklassen ein differenziertes Verhalten. n-Dialkylather werden unter Bildung von Alkoxysilanen und Alkylchlorid gespalten. Aliphatische Isoather werden anhydrisiert. Aromatische Ather bleiben unverandert. Fettaromatische Ather werden glatt gespalten. Bei diesen Athern tritt, sofern sie einen hoheren Alkylrest haben, eine zusatzliche Wanderung des Alkylrestes in den Benzolkern ein. Alkoxysilane werden durch Erhitzen mit Alkylhalogenid schnell in Oligobzw. Polysiloxane ubergefuhrt.