期刊
ORGANOMETALLICS
卷 35, 期 14, 页码 2367-2377出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.organomet.6b00348
关键词
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资金
- National Science and Engineering Research Council [2015-04634]
- University of Regina
- Government of Saskatchewan
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)Ph-2}]. 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 gamma-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.
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