PHOSPHINIMINES DERIVED FROM PHOSPHOLE DIMERS BY THE STAUDINGER REACTION

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Abstract
The Staudinger reaction of phenyl azide with the phosphine groups of phosphole dimers gives bis(phenylimino) derivatives. Hydrolysis or methanolysis leads to diphosphine dioxides with retention of configuration at the bridging phosphorus and inversion at the 2-phospholene phosphorus. This reaction is useful in providing access to a new isomeric form of the phosphole oxide dimer framework. Amines catalyze the rearrangement at the 2-phospholene phosphorus to the isomeric form which is commonly produced on dimerization of phosphole oxides. Amides also catalyze the inversion at the 2-phospholene group in the Staudinger product. Both the original and the rearranged Staudinger product were found to be reduced with trichlorosilane to give the same diphosphine.