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On [Na(POCl 3 ) 4 ] + Complex Ion Formation: Conductivity, Raman, and NMR studies in the system phosphoryl chloride–sodium tetrachloro aluminate and related compounds
Author(s) -
Birkeneder F.,
Berg R. W.,
Hjuler H. A.,
Bjerrum N. J.
Publication year - 1989
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.19895730117
Subject(s) - raman spectroscopy , electrolyte , conductivity , ion , nmr spectra database , solvent , salt (chemistry) , analytical chemistry (journal) , inorganic chemistry , materials science , chemistry , spectral line , organic chemistry , physics , electrode , astronomy , optics
The system POCl 3 –NaAlCl 4 was investigated by measuring the conductivity and the Raman and NMR spectra ( 27 Al, 23 Na and 31 P) as a function of the mol fraction x of NaAlCl 4 in POCl 3 . Additionally, Raman spectra of POCl 3 solutions of NaFeCl 4 , LiAlCl 4 , LiFeCl 4 , and KAlCl 4 were recorded. In solutions containing Li + or Na + ions a liquid to solid (or jelly) phase transition was observed under certain conditions, dependent on salt concentration and temperature. Observed changes in the Raman spectra of the electrolyte solutions in comparison to the pure solvent POCl 3 demonstrate the existence of interactions. Clearly, the POCl 3 eigenfrequencies and hence the molecules are pertubed. The formation of [M(POCl 3 ) 4 ] + complexes (M = Li, Na) can be deduced from the Raman measurements. NMR investigations support this conclusion. For assigning of Raman spectra, (Li + , K + ) cation and ([FeCl 4 ] − , [SbCl 6 ] − ) anion substitutions were employed.