Sequential Electrophilic Substitution Reactions of Tungsten-Coordinated Phosphenium Ions and Phosphine Triflates

Abstraction of chloride from [W­(CO)5{PPhCl2}] with AgOSO2CF3 leads to the phosphine triflate complex [W­(CO)5{PPhCl­(OSO2CF3)}] 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 AgOSO2CF3 leads, in most cases, to the respective phosphine triflates [W­(CO)5{PPhR­(OSO2CF3)}], which react with ferrocene to form the ferrocenyl phosphine complexes [W­(CO)5{PPhR­(C10H9Fe)}]. The W­(CO)5 unit can be removed via photolysis in the presence of bis­(diphenylphosphino)­ethane to form metal-free phosphines.