Da. Shultz et al., EFFECT OF ALIPHATIC AMINE BASES ON THE AGGREGATION OF ALKALI-METAL SALTS OF 3,5-DI-TERT-BUTYLSEMIQUINONE (3,5-DBSQ), Inorganic chemistry, 37(7), 1998, pp. 1540-1543
The alkali metal salts (Li+, Na+, K+) of 3,5-di-tert-butylsemiquinone
anion (3,5-DBSQ) have been prepared in the presence of three amine bas
es, triethylamine (TEA), tetramethylethylenedismine (TMEDA), and penta
methyldiethyltriamine (PMDTA), as well as in the absence of amine in t
wo solvents, toluene and THF. EPR spectral evidence shows that for M(3
,5-DBSQ), aggregation of the lithium and sodium salts is effectively p
rohibited by Lewis basic amines PMDTA and TMEDA, with the former being
mole effective than the latter. The EPR spectra of the least Lewis ac
idic metal ion, K+, are unaffected by addition of amines. In the absen
ce of amines, the coordinating solvent, THF, is effective at preventin
g aggregation, while substantial aggregation occurs in the noncoordina
ting solvent, toluene. The effectiveness of PMDTA is so great that M(3
,5-DBSQ) (M = Li+ and Na+) aggregation is prevented even in toluene. T
he combination of solution and frozen solution spectra is best for det
ermining the presence of aggregates due to aggregation-induced line br
oadening in solution spectra and fine structure in spectra of S > 1/2
species. The results of the frozen solution spectral studies indicates
that, for the amines studied, PMDTA is singular in its ability to pre
vent aggregation and Li+ and Na+ salts are best chelated by PMDTA. Fin
ally, we show the success of this method by preparing a solution of Na
2I that is stable for several hours and is amenable to EPR spectral ch
aracterization.