The cyclic trifluorophosphoranes, (CH2)nPF3(n = 4, 5; 1c and 1d) were found to react with 8-trimethylsiloxyquinoline (2) with cleavage of the SiO bond and formation of the mono-substituted derivatives, (CH2)nPF2(Ox), 4 and 5 (Ox = 8-oxyquinolyl). In the case of 4, intramolecular coordination between the nitrogen atom of the quinolyl group and phosphorus rendering phosphorus hexa-coordinate (λ6P) has been established by NMR spectroscopy (31P,19F). By contrast, this type of interaction between N and P is not observed in the case of 5 which is, therefore, a normal substituted fluorophosphorane with λ5P. Intramolecular coordination, involving λ6P, is observed, however, in the case of the products originating from the reaction of the trimethylsilyl ester of N,N-dimethylglycine, Me2NCH2C(:O)OSiMe3(6) with both PF5and PhPF4; it has been indicated for both 7 and 8 by NMR spectroscopy. In the case of 8, a single crystal X-ray structure determination has confirmed the intramolecular coordination between P and N, with the formation of hexa-coordinate phosphorus. © 1989.
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