Phosphorus–Carbon Bond Forming Reactions of Diphenylphosphenium and Diphenylphosphine Triflate Complexes of Tungsten

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• 作者：Arumugam Jayaraman ; Brian T. Sterenberg
• 刊名：Organometallics
• 出版年：2016
• 出版时间：July 25, 2016
• 年：2016
• 卷：35
• 期：14
• 页码：2367-2377
• 全文大小：624K
• 年卷期：0
• ISSN：1520-6041

文摘

The complex [W(CO)<sub>5sub>{PClPh<sub>2sub>}] reacts with AlCl<sub>3sub> to form a mixture of the phosphenium complex [W(CO)<sub>5sub>{PPh<sub>2sub>}][AlCl<sub>4sub>] and an isocarbonyl, with GaCl<sub>3sub> to form [W(CO)<sub>5sub>{PPh<sub>2sub>}][GaCl<sub>4sub>], and with silver trifluoromethanesulfonate to form [W(CO)<sub>5sub>{P(OSO<sub>2sub>CF<sub>3sub>)Ph<sub>2sub>}]. All three complexes react as strong P electrophiles, undergoing electrophilic substitution reactions with aromatic and heteroaromatic compounds, alkenes, and alkynes, to form aromatic and heteroaromatic phosphines, allyl phosphines, and alkynyl phosphines, respectively. Alkenes lacking cleavable γ-H atoms and internal alkynes undergo tandem electrophilic addition/substitution reactions, adding between the P and one of the phenyl rings to form fused P heterocycles. The newly formed phosphines can be removed from the tungsten complex by photolysis in the presence of bis(diphenylphosphino)ethane.