ON THE REACTION OF P(4)E(3)I(2) (E=S, SE) WITH SOME CARBOXYLIC-ACIDS AND DITHIOCARBAMIC ACIDS

Autor(en): BLACHNIK, R
HACKMANN, K
PEUKERT, U
Stichwörter: 3,5-ACYL(DITHIOCARBAMIDO)-2,6,7-TRICHALCOGENA-1,3,4,5-TETRAPHOSPHA-BIYCL O[2,2,1]HEPTAN; 3,6-ACYL-(DITHIOCARBAMIDO)-2,5,7-TRICHALCOGENA-1,3,4,6-TETRAPHOSPHA-BICY CLO[2.2.1]HEPTAN; 3-IOD-5-ACYL(DITHIOCARBAMIDO)-2,6,7-TRI-CHALCOGENA-1,3,4,5-TETRAPHOSPHA- BICYCLO [2.2.1]HEPTAN; 3-IOD-6-ACYL(DITHIOCARBAMIDO)2,5,7-TRICHALCOGENA-1,3,4,6-TETRAPHOSPHA-BI CYCLO[2.2.1]HEPTAN; 31P NMR; Chemistry; Chemistry, Inorganic & Nuclear; MAGNETIC-RESONANCE PARAMETERS; TETRAPHOSPHORUS TRISULFIDE
Erscheinungsdatum: 1995
Herausgeber: JOHANN AMBROSIUS BARTH VERLAG
Journal: ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE
Volumen: 621
Ausgabe: 7
Startseite: 1211
Seitenende: 1217
Zusammenfassung: 
By the reaction of alpha-P(4)E(3)I(2) (E = S, Se) with carboxylic acids, dithiobenzoic acid or dithiocarbamic acids in the presence of triethylamin or with (C6H5)(3)SnR, or of beta-P(4)E(3)I(2) with tin-organic compounds alpha-P(4)E(3)(I)R, alpha(beta)-P(4)E(3)R(2) [R = -OC(O)C6H5, -OC(O)CH3, -SC(S)NC5H10, -SC(S)N(C2H5)(2)], alpha-P4S3(I)SC(S)C6H5, alpha-P4S3(SC(S)C6H5)(2) and beta-P(4)E(3)(I)R (R = -OC(O)C6H5, -OC(O)CH3) were prepared in solution and identified by P-31 NMR spectroscopy. In addition alpha-P4S3(NC5H10)(SC(S)NC5H10) was detected. The beta-isomers could be obtained also with lesser yields by the reaction with the dithiocarbamic acids, too. The substitution of the second iodine ligand in beta-P(4)E(3)I(2) resulted mainly in beta-P4S3(R(exo))(2) and by inversion of the configuration at a phosphorus atom, in beta-P(4)E(3)R(exo)R(endo). alpha-P4S3I2 reacted with methanol in CS2 to alpha-P4S3(OCH3)(SC(S)OCH3) and alpha-P4S3(SC(S)OCH3)(2). The P-31 NMR data of the compounds are discussed. The P-31 NMR spectra of the alpha(beta)-P(4)E(3) dithiocarbamates indicate dynamic processes in the solution, e.g. alpha-P4S3(I)(SC(S)NR(2)) showed an intramolecular conversion, due to the anisobidentate dithiocarbamate ligand. This behaviour had not previously been noticed for compounds with a P4S3-skeleton.
ISSN: 00442313
DOI: 10.1002/zaac.19956210717

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