Nitrilohexaphosphonitrilic Chloride: A Chemical and Spectroscopic Study

Abstract

The preparation of nitrilohexaphosphonitrilic chlorideZ N,P6ClY is described; its infrared, Raman, mass and nuclear magnetic resonance spectra indicate a tricyclic condensed ring structure of GBa symmetry. The molecule decomposes on attempted substitution of the chlorine atoms by fluorine and by methoxy-groups, but with dimethylamine both addition and substitution take place. One central bond is broken, and a bridged ring imide N6P6(NH)(NMe2),CI, is formed, in which the ring structure is sufficiently rigid for axial and equatorial groups to be distinguished. The detailed molecular structure of N,P6C19 shows evidence of a compromise between the requirements for optimum o-and n-bonding, the central N-P bonds being strained. Its substitution behavior, base strength, ultraviolet spectrum, mass spectrum, and molecular geometry are interpreted in these terms.La preparation du chlorure de nitrilohexaphosphonitrilique2 N7P6Cly est decrite; ses spectres infrarouge, raman, resoriance magnetique et son spectre de masse indiquent une structure tricyclique condensCe de symetrie CBo. La mol6cule se decompose lorsqu'une substitution des atomes de chlore par les groupes fluor ou methoxy est tentee, avec la dimethylamine l'addition et la substitution ont lien toutes deux. Une liaison centrale se brise et un cycle imide ponte N6P6(NH)(NMe2)8C12 se forme, dans lequel la structure cyclique est suffisamment rigide pour pouvoir distinguer les groupes axial et equatorial. La structure moleculaire detaillee de N,P6CI, fournit la preuve d'un compromis entre un recouvrement optinal et necessaire des liaisons o et n et une tension des liaisons centrales N-P. Le comportement dans la substitution, la force basique, les spectres de masse et u.v., la geometrie mol~culaire de ce compose ont etC aussi interpretis en fonciion de ce facteur.[Traduit par le journal]Can. J. Chem., 51. 520 (1973)

Reference standards for negative ion mass spectrometry

“…The compound corresponding to n = 7 of the latter type has been isolated from depolymerization products of the polymer and the structure established to be a condensed ring (3). 3 The others of this type are also likely to have similar structures (4). These compounds have been observed in the positive ion mass spectra of cyclic c o m p o~n d s .~ As one possible mode of the formation, the elimination of phosphorus pentachloride has been suggested: (PNCl,), -+ P,-lN,C12,-, + PCI, Cyclic compounds are the main products in depolymerization, while condensed ring compounds are also produced in an appreciable quantity.…”

“…The compound corresponding to n = 7 of the latter type has been isolated from depolymerization products of the polymer and the structure established to be a condensed ring (3). 3 The others of this type are also likely to have similar structures (4). These compounds have been observed in the positive ion mass spectra of cyclic c o m p o~n d s .~…”