biostudies-literatureJayaraman ANatural Sciences and Engineering Research Council of CanadaUniversity of Regina7849-7861https://www.ebi.ac.uk/biostudies/studies/S-EPMC6645012biostudies-literatureUnknown2(11)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 <i>N</i>,<i>N</i>-diethylaniline, anisole, <i>N</i>,<i>N</i>-dimethyl-<i>p</i>-toluidine, toluene, biphenyl, naphthalene, 2,7,9,9-tetramethyl xanthene, and allyltrimethylsilane to form the chlorophosphine complexes [W(CO)₅{PPhClR}], where R = <i>p</i>-diethylanilinyl, <i>p</i>-anisyl, 2-(<i>N</i>,<i>N</i>-dimethyl-4-methylphenyl), <i>p</i>-tolyl, <i>p</i>-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.ACS omegaSequential Electrophilic Substitution Reactions of Tungsten-Coordinated Phosphenium Ions and Phosphine Triflates.PMC66450122015-04634Sterenberg BTJayaraman ANilewar SJacob TVfalseSequential 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 <i>N</i>,<i>N</i>-diethylaniline, anisole, <i>N</i>,<i>N</i>-dimethyl-<i>p</i>-toluidine, toluene, biphenyl, naphthalene, 2,7,9,9-tetramethyl xanthene, and allyltrimethylsilane to form the chlorophosphine complexes [W(CO)₅{PPhClR}], where R = <i>p</i>-diethylanilinyl, <i>p</i>-anisyl, 2-(<i>N</i>,<i>N</i>-dimethyl-4-methylphenyl), <i>p</i>-tolyl, <i>p</i>-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.2017-01-01T00:00:00Z2017 Nov2024-02-15T13:34:01.341Z2019-08-31T07:04:14ZS-EPMC66450123145734210.1021/acsomega.7b01424