Infrared study of the νOH stretching vibration of hydrogen bonded complexes involving phenol derivatives and thiocarbonyl bases. Comparison with carbonyl bases
✍ Scribed by D. Reyntjens-Van Damme; TH. Zeegers-Huyskens
- Publisher
- Wiley (John Wiley & Sons)
- Year
- 2010
- Weight
- 415 KB
- Volume
- 88
- Category
- Article
- ISSN
- 0037-9646
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✦ Synopsis
The formation enthalpy, the frequency shift and integrated intensity of the '.'OH stretching vihration have heen determined for hydrogen bonded complexes formed between phenol derivatives and tetramethylthiourea or dimethylthioformamide. These data are compared with comnlexes involving carhonyl hases. The results suggest that, at constant -A l l values, more charge is transferred to the o(OI1) bond with thiocarbonyl bases; this is in qualitative agreement with the far infrared results and the theoretical predictions.
INTRODIJCT ION
The hydrogen honded com!>lexes involving hydroxyl derivatives and carbonyl bases have heen extensively studied hy infrared spectroscopy, but so far only meager experimental results are available for sulfur hases. Some spectrometric or thcrmodynamic results have however been reported for the interaction of proton donors with sulfides' 3 2 , trialkylphosphine sulfides3, triethylthiop h ~s p h n t e ~' ~ ' 6 , tctramcthyl thiourea7 r 8 and h e x a m e t h y l p h o s n h o r o t h i o i c triamide'l. are available. In this work, we report a study of the thermodynamic (enthalpy of complex Cormationl and spectroscopic (frequency shift and intensity of the vOH vibration) properties o r hydrogen bonded complexes involving phenol derivatives and tetramethylthiourea (TMTIJ) or dimethylthioformamide (IP4TF). These parameters will he compared with those previously reported for hydrogen bonds involving carbonyl hases.
But so far, no intensity data of the v O t I . . . S stretching vibration EXPERIMENTAL A l l measurements were performed using C C 1 4 as solvent. The infrared spectra were recorded on the P.E. 325 spectrophotometer Thc phenol concentration varied between lo-' and M to prevent self-association and the base concentrations ranged from The temperature of the solutions was measured with a thermistor immersed using an extended scale.