Amino and mu-imino tetraphosphorus trisulfide compounds: NMR evidence for invertomers and bridged cages with an alpha- or beta-P4S3 skeleton

Autor(en): Blachnik, R
Hackmann, K
Tattershall, BW
Stichwörter: Chemistry; Chemistry, Inorganic & Nuclear; CONSTANTS; Crystallography; MAGNETIC-RESONANCE PARAMETERS; P-31; PHOSPHORUS; SPECTRA; STEREOCHEMISTRY
Erscheinungsdatum: 1996
Herausgeber: PERGAMON-ELSEVIER SCIENCE LTD
Journal: POLYHEDRON
Volumen: 15
Ausgabe: 9
Startseite: 1415
Seitenende: 1427
Zusammenfassung: 
Reaction of alpha- or beta-P4S3I2 with RNH(2) (R = H, Me, Bu(t) or Ph) led to new imino-bridged cage skeletons in alpha- or beta-P4S3(mu-NR), as well as both exo,exo- and endo,exo-isomers of either alpha- or beta-P4S3(NHR)(2) (except for R = H). Cage compounds P4S2(mu-NR) (R = Bu(t) or Ph) and alpha-P4S2(mu-NR)(2), with structures analogous to P4S3 and alpha-P4S4, respectively,have been identified as decomposition products. The new compounds were characterised in solution by full analysis of their P-31 NMR spectra. The configuration at bridging nitrogen in alpha-P4S3(mu-NR) was planar. An ab initio computation of molecular geometry of alpha-P4S3(mu-NH) is reported. Mechanistic arguments are advanced to rationalise the formation of isomers endo,exo-alpha-P4S3(NHR)(2), in contrast to corresponding reactions with secondary amines, which give only exo,exo-alpha-P4S3(NR(1)R(2))(2).
ISSN: 02775387
DOI: 10.1016/0277-5387(95)00414-9

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