Competitive or sequential reaction of an electrophilic terminal phosphinidene metal(0) complex with allyl halides? [2+1]-cycloaddition vs. C–X bond insertion

Abstract

The transiently generated electrophilic terminal phosphinidene complex [(CO)₅WPCH(SiMe₃)₂] 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 ³¹P{¹H} NMR spectroscopy. DFT calculations revealed that a novel rearrangement of transient phosphirane complexes is responsible involving C → P X atom transfer.