Synthesis of cyclenphosphoranes with polyfluorophenyl substituents; an X-ray structure of N-methyl cyclen-p-(heptafluorotolyl)phosphorane

The metathesis reactions between the lithiated derivative of cyclenphosphor ane (2) and octafluorotoluene, hexafluorobenzene, pentafluorobenzonitrile, pentafluoronitrobenzene, pentafluoro-n-butylbenzene, pentafluorobenzene and p-(cyanotetrafluorophenoxy-pentafluorobenzene) under re flux conditions ga ve cyclen-p-(heptafluorotolyl)phosphorane (3), cyclen-p-(pentafluorophenyl) phosphorane (4), cyclen-p-(cyanotetrafluorophenyl)phosphorane (5), cyclen-p -(tetrafluoronitrophenyl)phosphorane (6), cyclen-p-(n-butyltetrafluoropheny l)phosphorane (7), cyclen-p-(tetrafluorophenyl)phosphorane (8) and cyclen-p -(p-cyanotetrafluoro-phenoxytetraflurophenyl)phosphorane (9), respectively, in good yields. All products were characterized by spectral and analytical techniques. These materials are moderately stable thermally but are moistu re sensitive, hydrolyzing to form cyclen phosphine oxide (10). Addition of CH3I to 3 affords the phosphoammonium iodide (11). The X-ray crystal struct ure of 11 was obtained. The crystal is triclinic with a space group PI. The unit cell parameters a = 7.8652(2) Angstrom, b = 8.584(2) Angstrom, c = 22 .1573(3) Angstrom; alpha = 80.9010(10)degrees; beta = 79.2490(10)degrees; g amma = 76.9930(10)degrees; and Z = 2. (C) 1999 Elsevier Science S.A. All ri ghts reserved.