메뉴 건너뛰기




Volumn 126, Issue 34, 2004, Pages 10667-10675

O-H bond dissociation enthalpies in oximes: Order restored

Author keywords

[No Author keywords available]

Indexed keywords

CHEMICAL BONDS; DISSOCIATION; ELECTRONS; ENTHALPY; HYDROGEN; PYROLYSIS;

EID: 4344561879     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja047566y     Document Type: Article
Times cited : (58)

References (78)
  • 2
    • 4344634867 scopus 로고    scopus 로고
    • note
    • References to this rather extensive literature will be given only to those publications that are directly relevant to subjects at issue in the present article.
  • 8
    • 4344624518 scopus 로고    scopus 로고
    • note
    • Estimated spin density on nitrogen = 41 ± 5% in an orbital whose p/s ratio is 6.1 ± 0.7; see ref 9.
  • 11
    • 4344694306 scopus 로고    scopus 로고
    • note
    • To distinguish them from the more common class of π radicals in which the unpaired electron is in an orbital perpendicular to the local molecular framework.
  • 23
    • 4344620028 scopus 로고    scopus 로고
    • Reference 16
    • The sources of error we have identified in Bordwell et al.'s. EC-measured O-H BDEs for phenols and N-H BDEs for anilines have been described: (a) Reference 16.
  • 29
    • 4344612793 scopus 로고    scopus 로고
    • See footnote a, Table 1
    • See footnote a, Table 1.
  • 35
    • 4344695098 scopus 로고    scopus 로고
    • note
    • This revision has important implications since the calorimetric O-H BDE in 2,4,6-tri-tert-butylphenol of 81.24 kcal/mol26 has been used as the standard for all BDEs determined by the REqEPR technique,17d.27 and hence, all of these BDEs should be revised downward by 1 kcal/mol (and even lower for many phenols because of H-bonding to the benzene solvent used for REqEPR measurements).28 Interestingly, the 1 kcal/mol downward revision of the O-H BDE in phenol and α-tocopherol yields values of 87.3 and 77.3 kcal/mol, respectively, in full agreement with the results obtained by photoacoustic calorimetry.16.29
  • 42
    • 4344699258 scopus 로고    scopus 로고
    • note
    • These corrections to REqEPR-derived BDEs will be detailed in a forthcoming article.
  • 51
    • 4344686058 scopus 로고    scopus 로고
    • note
    • Estimated from data given in ref 16 for the phenol-benzene hydrogen bond.
  • 57
    • 4344564702 scopus 로고    scopus 로고
    • note
    • Since 443 K is just above the boiling point of tert-butylbenzene, reaction times were not shortened by raising the temperature for reasons of safety.
  • 58
    • 4344647134 scopus 로고    scopus 로고
    • note
    • 3 In the data analysis, a pre-equilibration time was used to compensate for this feature.
  • 59
    • 4344662555 scopus 로고    scopus 로고
    • note
    • ..4.12 The probable mechanisms by which these compounds are formed have been described.12 At least some of these products were present after heating the O-benzyl oxime ethers to 443 K for many weeks, but since they provide no useful information they will be ignored henceforth.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.