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A reaction scheme has been devised according to 3 RX + 3 Ti(III) + 0.25 P₄ → PR₃ + 3 XTi(IV), wherein RX = PhBr, CyBr, Me₃SiI or Ph₃SnCl, with contrasting results in the case of more hindered RX. The scheme accomplishes the direct radical functionalization of white phosphorus without the intermediacy of PCl₃

Radical synthesis of trialkyl, triaryl, trisilyl and tristannyl phosphines from P4