B. Twamley, C. D. Sofield, M. Olmstead
Mar 30, 1999
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Journal
Journal of the American Chemical Society
Abstract
The synthesis and characterization of several m-terphenyl heavier main group 15 (P, As, Sb, or Bi) dihalides, together with their reduction to give a homologous series of double-bonded dipnictenes, are reported. Reaction of LiC6H3-2,6-Mes2 (Mes = C6H2-2,4,6-Me3) or LiC6H3-2,6-Trip2 (Trip = C6H2-2,4,6-iPr3) with the appropriate trihalide affords 2,6-Mes2H3C6ECl2 (E = As, 1; Sb, 2; Bi, 3) and 2,6-Trip2H3C6ECl2 (E = P, 4; As, 5; Sb, 6; Bi, 7). The compounds 1−7 were characterized by 1H and 13C NMR spectroscopy as well as by 31P NMR spectroscopy in the case of 4. In addition, the structures of 3, 5, and 6 were determined. Reduction of the phosphorus species 4 with potassium in hexane gives a mixture of the diphosphene 2,6-Trip2H3C6PPC6H3-2,6-Trip2, 12, and the phosphafluorene species, 1-(2,4,6-triisopropylphenyl)-5,7-diisopropyl-9-phosphafluorene, 11. The compound 11, which results from the insertion of a phosphorus into a C(Ar)−C(i-Pr) bond was synthesized in higher yield by the reduction of 4 with magnesium...