High-pressure Fourier transform micro-Raman spectroscopic investigation of diiodine-heterocyclic thioamide adducts.
The pressure dependences of the Fourier transform micro-Raman spectra of four heterocyclic thioamides [[(bztzdtH)I2] x I2] (1) (bztzdtH = benzothiazole-2-thione), [(bztzdtH)I2] (2), [[(tzdtH)2I+] x I3- x 2I2] (3) (tzdtH = thiazoline-2-thione), and [[(bzimtH)I2]2 x I2 x 2H2O] (4) (bzimtH = benzimidazole-2-thione) have been studied between ambient pressure and 50 kbar. For 1, generation of I3- ions through disproportionation reactions is evident as the pressure is increased. There are empirical linear correlations between the frequency and (I-I) bond length and the applied pressure. The iodine adduct of thioamide 2 is more sensitive to pressure when compared to the 1 or 4 iodine adducts. This difference in behavior may be attributed to differences in crystal structures or to a lower I-I bond order. Monitoring of other vibrational transitions of the thiomide structure reveals several less important pressure dependences.
dos Santos
João Henrique Z
JH
Department of Chemistry, McGill University, Montreal, Que., Canada. jhzds@iq.ufrgs.br
Butler
Ian S
IS
Daga
Vasiliki
V
Hadjikakou
Sotiris
S
Hadjiliadis
Nick
N
D005583:Fourier Analysis; D006571:Heterocyclic Compounds / Q000737:chemistry; D017613:Iodine Compounds / Q000737:chemistry; D008853:Microscopy; D011312:Pressure; D013059:Spectrum Analysis, Raman / Q000295:instrumentation / Q000379:methods*; D013854:Thioamides / Q000737:chemistry*
D006571:Heterocyclic Compounds; D017613:Iodine Compounds; D013854:Thioamides