Tertiary phosphine oxides are prepared under mild conditions by sequen
tial addition of diphenyl-phosphinoyl chloride to divalent samarium co
mpounds (SmCp(2) and SmI2) followed by reaction with various electroph
iles such as organic halides, tosylates, epoxides or alpha,beta-unsatu
rated ketones. Biscyclopentadienylsamarium (SmCp(2)) gives better yiel
ds than SmI2. Similar reactions, using phenylphosphonoyl dichloride, S
mI2 and subsequent addition of two equivalents of activated halides, y
ield the corresponding tertiary phosphine oxides.