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Abstract

The treatment of bis[(dialkylamino)cyclopropenimines] with dihalophosphines in the presence of trimethylsilyl trifluoromethanesulfonate (TMSOTf) to form diimine-stabilized P^III-centered dications is reported. The structures of the new compounds were determined by using X-ray diffraction analysis and their donor abilities as ligands evaluated through electrochemical methods. Despite the two positive charges that they bear, these compounds depict intermediate behavior between that of phosphines and phosphites. The coordination of the [L₂PR]²⁺ moiety to Au^I and Ag^I is also reported. Even more surprisingly, these phosphorus centers can be oxidized to the corresponding P^V dications in the presence of strong oxidants such as peroxides or XeF₂.