The transiently generated electrophilic terminal phosphinidene complex [(CO)WPCH(SiMe)] reacted with allyl halides (X = F, Cl, Br) in toluene resulting in the formation of stable C-X insertion products 3a-c and diastereomeric phosphirane complexes 4a,a',b,b' as well as methylenephosphirane complex 5 as observed by P{H} NMR spectroscopy. DFT calculations revealed that a novel rearrangement of transient phosphirane complexes is responsible involving C → P X atom transfer.
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