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.以三氟甲磺酸银(AgOSO2CF3)从配合物[W(CO)5{PPhCl2}]中夺取氯离子，可得到三氟甲磺酰氧基膦配合物[W(CO)5{PPhCl(OSO2CF3)}]。该配合物可与N,N-二乙基苯胺、苯甲醚、N,N-二甲基对甲苯胺、甲苯、联苯、萘、2,7,9,9-四甲基呫吨及烯丙基三甲基硅烷发生亲电取代反应，生成氯膦配合物[W(CO)5{PPhClR}]，其中R分别为对二乙基苯胺基、对茴香基、2-(N,N-二甲基-4-甲基苯基)、对甲苯基、对联苯基、1-萘基、4-(2,7,9,9-四甲基呫吨基)及烯丙基。再次以三氟甲磺酸银夺取第二个氯离子时，多数情况下可得到对应的三氟甲磺酰氧基膦配合物[W(CO)5{PPhR(OSO2CF3)}]；此类配合物可与二茂铁反应，生成二茂铁基膦配合物[W(CO)5{PPhR(C10H9Fe)}]。可在双(二苯基膦)乙烷(bis(diphenylphosphino)ethane)存在下通过光解脱除W(CO)5单元，得到无金属膦化合物。