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

ion 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.