REACTION DES PHOSPHOLES AVEC LES METAUX CARBONYLES SOUS PRESSION D'OXYDE DE CARBONE. OBTENTION DE COMPLEXES DERIVES DES PHOSPHOLES-2H

Article abstract of DOI:10.1016/0022-328X(84)85010-X

Above 150 deg C, 1-phenyl-3,4-dimethylphosphole (1) is in equilibrium, through phenyl and hydrogen <1,5> shifts, with 5-phenyl-3,4-dimethyl-2H-phosphole (3).If the reaction of 1 with metal carbonyls is run under a CO pressure high enough to prevent the formation of phosphorus-metal bonds below 150 deg C, the metal carbonyls do not react with 1 but preferentially with 3.Around 150 deg C, complexes derived from <4+2> Diels-Alder dimers of 3 are obtained in the presence of W(CO)6 and Cr(CO)6 and these complexes are described.Around 160 deg C, phosphido-bridged complexes are formed with 2-phenyl-3,4-dimethylphospholyl acting as the P-donor and Mo(CO)6 and W(CO)6 and the products are described.Above 170 deg C still another type of phosphido-bridged complexes is obtained with 2-phenyl-3,4-dimethyl-4,5-dihydrophospholyl acting as the P-donor and Cr(CO)6 which is also described.The results are used for devising an optimized synthesis of 2-phenyl-3,4-dimethyl-1-phosphaferrocene from 1 and 2 at 160 deg C under CO pressure. 2-Phenyl-1-phosphaferrocene is similarly prepared from 1-phenylphosphole.