In situ-Erzeugung von [PX] und Insertion in (tBuP)3, (X = Cl,Br) Synthese der funktionalisierten Cyclophosphane (tBuP)3PX, [-(tBu)(X)P-2,3,4-(tBu)3]P4und Strukturbestimmung von (tBuP)3PCl

In situ Generation of PX] and Insertion into (^tBuP)₃, (X = Cl, Br). Synthesis of the Functionalized Cyclophosphanes (^tBuP)₃PX, 1-(^tBu)(X)P-2,3,4-(^tBu)₃]P₄ and Structure Analysis of (^tBuP)₃PCl The redox system PX₃/SnX₂ (X = Cl, Br) can be used as a source for the in situ generation of halogenphosphanediyl PX]. In the presence of tri-t-butylcyclotriphosphane (^tBuP)₃ the intermediately formed PX] is added to a ring P atom followed by an insertion reaction, which leads to a ring expansion, whereby monohalogenocyclotetraphosphanes (^tBuP)₃PX (X = Cl, Br; 1, 2 ) are formed. Excess PX] does not lead to further ring expansion but through a complex reaction course to the functionalized cyclotetraphosphanes 1-(^tBu)(X)P-2,3,4-(^tBu)₃]P₄, 3 (X = Br); 7 (X = Cl). 1, 2 and 3 could be obtained in a pure form and NMR and mass spectroscopically, 7 ³¹P-NMR spectroscopically, characterized. For 1 and 7 ³¹P? ^35,37Cl-isotopic shifts could be identified. 1 was further characterized by an X-ray structure analysis.