Beiträge zur Chemie des Phosphors, 45. Triphenyl‐cyclotriphosphan ‐ ein Derivat des P₃H₃

Abstract

Triphenyl‐cyclotriphosphan‐dikalium (2) wird lösungsmittelfrei bei der Metallierung von Pentaphenyl‐cyclopentaphosphan (3) mit der stöchiometrischen Menge Kalium in Benzol erhalten, außerdem durch Fällung der entsprechenden Reaktionslösung in Tetrahydrofuran mit Toluol oder Petroläther. Beim Abziehen des Solvens zur Trockene wird dagegen 2 · THF gebildet. 2 bzw. 2 · THF reagieren mit Jod bei − 78 °C zu den Verbindungen K2(CSH5P)3J2 (4) bzw. 4 · THF. Diese zerfallen in Lösung in Kalium‐jodid und das bisher nicht bekannte Triphenyl‐cyclotriphosphan (1), daa rein isoliert werden konnte. 1 unterscheidet sich von 3 durch das charakteristische Schmelzverhalten und das osmometrische Molekulargewicht sowie vor allem durch das IB‐ und Massenspektrum. Es ist bei − 20°C mehrere Wochen beständig, lagert sieh aber leicht ‐ vor allem bei etwas höherer Temperatur ‐ in das stabilere 3 urn.

A selective route to aryl-triphosphiranes and their titanocene-induced fragmentation

“…To the best of our knowledge, only four aryl-substituted triphosphiranes are reported in the literature. P 3 Ph 3 was described as early as 1973 as a labile solid with respect to P 5 Ph 5 ,20 and it has been shown that this compound is part of an equilibrium mixture consisting of different oligomers with ring sizes of n = 3, 4, 5, 6 21. Tokitoh et al synthesized (Anth = 9-anthryl, Bbt = 2,6-bis[bis-(trimethylsilyl)methyl]-4-[tris(trimethylsilyl)phenyl]) in good yield by heating a mixture of AnthPPBbt and n Bu 3 PTe 22.…”

Preparation of the Trinuclear Triphenylcyclotriphosphane Complex (C6H5)3P3[Mn(CO)2C5H5]3 by Demetalation of C5H5(CO)2MnP(C6H5)Li2

“…wt. 383 (MS); yield 290mg (11 %).--In an analogous way, without addition of cyclohexylamine, initial red coloration is followed by formation of a yellow reaction solution from which a mixture of (3) and ( 4 ) can be separated by sublimation (8OoC/10-torr) after removal of solvent.…”

“…The main reason is to be found in the ready decomposition of thioanions such as WSi-, MoSi-, and VSZ-to form metal sulfides when their aqueous solutions are acidified [4], and in the lower proton affinity of thioanions compared to oxoanions (protonation of the anion is assumed as the initial step of polyanion formation) which necessitates higher H + concentrations for polythioanion formation.…”

“…Pure ( 4 ) could not be prepared since this complex decomposeswithdisproportionation into(I)and ( 3 ) evenat -30°C during attempted chromatographic purification. However, C S H S ( C O )~M~P ( C~H~) ( H ) N H C~H~ 1 (5) can be obtained as a very stable derivative of ( 4 ) if cyclohexylamine is added to the mixture at the begining of the reaction. (5) is stable towards air even at room temperature ; a-elimination of C6H11NH2 is not observed even under more drastic conditions.…”