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

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journal contribution
posted on 13.07.2016, 11:33 by Arumugam Jayaraman, Brian T. Sterenberg
The complex [W­(CO)5{PClPh2}] reacts with AlCl3 to form a mixture of the phosphenium complex [W­(CO)5{PPh2}]­[AlCl4] and an isocarbonyl, with GaCl3 to form [W­(CO)5{PPh2}]­[GaCl4], and with silver trifluoromethanesulfonate to form [W­(CO)5{P­(OSO2CF3)­Ph2}]. 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.