钨配位磷鎓离子与三氟甲磺酸膦的顺序亲电取代反应

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

作者信息

Jayaraman Arumugam, Nilewar Shrikant, Jacob Tyler V, Sterenberg Brian T

机构信息

Department of Chemistry and Biochemistry, University of Regina, 3737 Wascana Parkway, Regina, Saskatchewan S4S 0A2, Canada.

出版信息

ACS Omega. 2017 Nov 14;2(11):7849-7861. doi: 10.1021/acsomega.7b01424. eCollection 2017 Nov 30.

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

[W(CO){PPhCl}]与AgOSOCF反应生成膦三氟甲磺酸盐配合物[W(CO){PPhCl(OSOCF)}]，该配合物与二乙苯胺、苯甲醚、二甲基对甲苯胺、甲苯、联苯、萘、2,7,9,9 - 四甲基呫吨和烯丙基三甲基硅烷发生亲电取代反应，形成氯膦配合物[W(CO){PPhClR}]，其中R = 二乙苯胺基、苯甲氧基、2 - (二甲基 - 4 - 甲基苯基)、对甲苯基、苯基苯基、1 - 萘基、4 - (2,7,9,9 - 四甲基呫吨基)和烯丙基。在大多数情况下，用AgOSOCF脱去第二个氯原子会生成相应的膦三氟甲磺酸盐[W(CO){PPhR(OSOCF)}]，其与二茂铁反应形成二茂铁基膦配合物[W(CO){PPhR(CHFe)}]。在双(二苯基膦基)乙烷存在下，通过光解可以除去W(CO)单元，形成无金属膦。