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Volumn 121, Issue 1, 1999, Pages 218-226

Solvent effects on the barrier to C - N bond rotation in N,N- dimethylaminoacrylonitrile

Author keywords

[No Author keywords available]

Indexed keywords

ACETONE; ACRYLONITRILE; CHLOROFORM; DICHLOROMETHANE; METHANOL; NITROMETHANE;

EID: 84962339692     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja982304f     Document Type: Article
Times cited : (33)

References (100)
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    • note
    • Since there is no way to correlate the two different transition states of DMF with those of DMAAN, we have simply used the average of the values reported for the two DMF transition states. The differences in the thermodynamic corrections for methyl rotation and nitrogen inversion between the two DMF transition states are extremely small (less than 0.05 kcal/mol).
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    • The values given here (5.1 kcal/mol for vinylamine, 7.5 kcal/mol for DMAAN) are calculated enthalpies at 0 K.
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    • note
    • It is worthy of note that the data point for acetonitrile in Figure 3 lies somewhat above the best fit line, indicating a higher barrier than in other solvents having comparable values for the Onsager dielectric function. This deviation possibly indicates that acetonitrile, like the aromatic and chlorinated solvents, yields somewhat stronger than expected interactions with polar solutes due to unusually great electronic polarizability. The "soft" π-system of acetonilrile could certainly account for such polarizability. A similar pattern was observed with DMA and DMF previously, where again acetonitrile yielded a somewhat stronger solvent effect than did acetone.
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    • "Polarity" here is meant as measured by the Onsager dielectric function.
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.