In the presence of chloride abstractors, metal-coordinated chlorophosphines undergo facile room-temperature electrophilic substitution reactions with unsaturated organic substrates, leading to P-C bond formation. This methodology can be applied sequentially two or three times, stepwise or in one-pot reactions, to form phosphines with three different substituents. The reactions are rapid and high-yielding, and can be applied to a wide range of organic substrates, making them valuable tools for P-C bond formation.

ion of chloride from [W(CO) 5 {PPhCl 2 }] with AgOSO 2 CF 3 leads to the phosphine triflate complex [W(CO) 5 {PPhCl(OSO 2 CF 3 )}] which undergoes electrophilic substitution reactions with N , N -diethylaniline, anisole, N , N -dimethyl- p -toluidine, toluene, biphenyl, naphthalene, 2,7,9,9-tetramethyl xanthene, and allyltrimethylsilane to form the chlorophosphine complexes [W(CO) 5 {PPhClR}], where R = p -diethylanilinyl, p -anisyl, 2-( N , N -dimethyl-4-methylphenyl), p -tolyl, p -phenylphenyl, 1-naphthyl, 4-(2,7,9,9-tetramethylxanthyl), and allyl. Abstraction of the second chloride with AgOSO 2 CF 3 leads, in most cases, to the respective phosphine triflates [W(CO) 5 {PPhR(OSO 2 CF 3 )}], which react with ferrocene to form the ferrocenyl phosphine complexes [W(CO) 5 {PPhR(C 10 H 9 Fe)}]. The W(CO) 5 unit can be removed via photolysis in the presence of bis(diphenylphosphino)ethane to form metal-free phosphines.