INVESTIGATION INTO SULFIDES AND SELENIDES OF PRIMARY PHOSPHINES - THE(1-HYDROXYALKYL)-ORGANYL-PHOSPHINE SULFIDES AND SELENIDES, NEW CLASSES OF COMPOUNDS

Primary phosphines react with S8 and Se8, respectively, forming organy lphosphine monosulfides, and monoselenides, respectively, RP(X)H2 (X = S, Se) which are well characterized by P-31 NMR spectroscopy. Organyl phosphine monosulfides are detected in the reaction mixture of primary phosphines with diaryl-1,3,2,4-dithiadiphosphetane-2,4-disulfides, to o. The reaction of primary phosphines with sulfur or selenium proceeds in presence of most of the ketones without formation of any side prod uct. The (1-hydroxyalkyl)-organyl-phosphine sulfides and selenides, re spectively, RP(X)(H)C(OH)R1R2, are yielded generally in crystalline fo rm. The X-ray crystal structure analysis of the (1-hydroxy-1-methyl-et hyl)-phenyl-phosphane sulfide (R = Ph, R1 = R2 = Me) has shown that in the crystal the molecules are chained via intermolecular 0-H ... S hy drogen bridging bonds (O ... S = 328 pm). Aldehydes react with primary phosphines and sulfur forming bis(I-hydroxyalkyl)-phenyl-phosphine su lfides, RP(S)[CH(OH)R1]2. H-1, C-13 , and P-31 NMR spectroscopic inves tigations allow to detect and to identify stereoisomers in some cases. Quantumchemical calculations reflect correctly which of the carbonyl compounds are able to react with the organylphosphine monosulfide form ed as intermediate.