Notizen: Die Schwingungsspektren der trimeren und tetrameren Phosphornitrilhalogenide

Abstract

Bei Untersuchungen an den penta-und hexameren Phosphornitrilhalogeniden wurden wir auf Unvoll kommenheiten der den trimeren und tetram eren Ver bindungen gewidmeten Arbeiten aufmerksamWir wiederholten deshalb die über die C hloride2> 3 und F lu o rid e4 publizierten Untersuchungen und bezogen die Bromide ein. Zum Beispiel ist die sehr starke, polarisierte Linie bei 100 cm-1 2 absolut nicht vorhanden und erscheint aber auch in einem anderen Spektrum aus dem gleichen Laborato rium 6 -um so merkwürdiger, daß D a a s c h 3 sie als ss. und polarisiert angibt.Unsere Ergebnisse finden sich in den Tabellen 1 und 2.Bei allen Verbindungen weisen die Spektren ziemlich sicher das Vorliegen ebener (P N )3-bzw. (P N )4-Ringe zumindest für die freien Molekeln in Lösungen oder Schmelzen aus. Eine nähere Diskussion sowie experi mentelle Einzelheiten werden anderenorts veröffentlicht.

Nitrilohexaphosphonitrilic Chloride: A Chemical and Spectroscopic Study

“…However, in N3P,C16 the totally its infrared activity indicating the absence of symmetric ring breathing frequency is established a horizo~ltal symmetry plane. v,(PCl,),,,, is then at 783-785 cm-' (10,11,14,15,17,18), and the either at 503 or 525 cm-' ; the latter seems more likelihood that N7P6CI, contains 6-membered likely by comparison with the spectra of the rings is reinforced by the occurrence of a Raman trimeric chloride-fluorides (14), b~l t a degenerate line at 661 cm-' ; a totally syn~n~etric band, attribdeformation mode of the N,P, ring has been uted to a trigonal ring deformation, appears as assigned near this frequency (10,11,13,17), and a strong polarized band in the Raman spectrum these two ass~gnments could be reversed. The of N3P,C16 at 669-671 cmP1 (11,15,17,18).…”

“…N,P3C1,: 363 (13); 365 (14, there is no close line in the spectra of either 15,17,18). N,P,CI,~.~: 385, 413 (12); 387, 413 N6P,C1,, (16) or N,P,CI,, (15,16), and al-(15);404 (13).N,P5C1,,:439(15).N6P6Cl,,:461 though there is a line at 782-785 cm-' in the (16)'; 451 , . ~e therefore assign the strong Raman Raman spectrum of N4P4CI, (12,13,15,20), it lines at 442 cm-I in N,P6C19 to v,(PC~,)~,,,, is depolarized.…”

“…N,P,CI,~.~: 385, 413 (12); 387, 413 N6P,C1,, (16) or N,P,CI,, (15,16), and al-(15);404 (13).N,P5C1,,:439(15).N6P6Cl,,:461 though there is a line at 782-785 cm-' in the (16)'; 451 , . ~e therefore assign the strong Raman Raman spectrum of N4P4CI, (12,13,15,20), it lines at 442 cm-I in N,P6C19 to v,(PC~,)~,,,, is depolarized. However, in N3P,C16 the totally its infrared activity indicating the absence of symmetric ring breathing frequency is established a horizo~ltal symmetry plane.…”

“…The two lowest may correspond to the 157, 172 cm-I Raman lines in N,P,C16 (13) which are there of species E", characteristic of PCi, rocking and torsional vibrations. The line at 332 cm-' seems the natural choice for G(PCl,)i,p,, but an out-of-plane ring deformation is also expected in this region.…”