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Volumn 122, Issue 22, 2000, Pages 5251-5257

Topochemical dihydrogen to covalent bonding transformation in LiBH4·TEA: A mechanistic study

Author keywords

[No Author keywords available]

Indexed keywords

LITHIUM DERIVATIVE; TRIETHANOLAMINE;

EID: 0034616877     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja994361u     Document Type: Article
Times cited : (30)

References (73)
  • 44
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    • note
    • 11a (13) This transformation occurs faster (∼4 days) if 2 is heated as a suspension in DMSO.
  • 48
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    • note
    • -.
  • 49
    • 84934609096 scopus 로고
    • Treatise On Solid State Chemistry; Plenum Press: New York
    • (a) Hannay, N. B. Reactivity of Solids; Treatise On Solid State Chemistry; Plenum Press: New York, 1976; Vol 4.
    • (1976) Reactivity of Solids , vol.4
    • Hannay, N.B.1
  • 62
    • 0342793408 scopus 로고    scopus 로고
    • note
    • At temperatures above 120 °C, the solid-state decomposition of 1 becomes faster than predicted by the Arrhenius equation. A possible explanation is that the dissipation of the resulting heat becomes too slow compared to decomposition rate, eventually leading to the autoacceleration of reaction. No melting occurs even under these conditions, as verified by optical microscopy.
  • 63
    • 0343227975 scopus 로고    scopus 로고
    • note
    • 0,i is set for α = 0.1, the resulting activation energies vary between 14.9 and 24.1 kcal/mol. In comparison, the Avrami-Erofeyev (n = 2) model analysis does not show much variation. Considering also the fact that it fits our data much better than any other model, and is in agreement with the microscopic observations and available structural data for 1, we think that the use of this model is particularly appropriate for the present study.
  • 64
    • 33748538977 scopus 로고
    • For other solid-state reactions where the kinetics are directly coupled to chemical transformations see, for example: (a) Galwey, A. K.; Mohamed, M. A. J. Chem. Soc., Faraday Trans. 1985, 81, 2503. (b) Son, S. F.; Asay, B. W.; Henson, B. F.; Sander, R. K.; Ali, A. N.; Zielinski, P. M.; Phillips, D. S.; Schwarz, R. B.; Skidmore, C. B. J. Phys. Chem. B 1999, 103, 5434.
    • (1985) J. Chem. Soc., Faraday Trans. , vol.81 , pp. 2503
    • Galwey, A.K.1    Mohamed, M.A.2
  • 67
    • 0001510427 scopus 로고
    • 5 intermediate (see, for example: Schreiner, P. R.; Schaefer, H. F., III; Schleyer, P. v. R. J. Chem. Phys. 1994, 101, 7625). In the solution the four-center transition state could be unambiguously eliminated based on kinetic isotope effects and hydrolysis experiments in the presence of trimethylammonium ion (Davis, R. E. J. Am. Chem. Soc. 1962, 84, 892), but in our solid-state system the possibility of a concerted mechanism cannot be ruled out. However, considering the similarity of the reacting partners and the activation parameters found in our study and in solution, it appears the same mechanism should apply for both.
    • (1994) J. Chem. Phys. , vol.101 , pp. 7625
    • Schreiner, P.R.1    Schaefer H.F. III2    Schleyer, P.V.R.3
  • 68
    • 33947478873 scopus 로고
    • 5 intermediate (see, for example: Schreiner, P. R.; Schaefer, H. F., III; Schleyer, P. v. R. J. Chem. Phys. 1994, 101, 7625). In the solution the four-center transition state could be unambiguously eliminated based on kinetic isotope effects and hydrolysis experiments in the presence of trimethylammonium ion (Davis, R. E. J. Am. Chem. Soc. 1962, 84, 892), but in our solid-state system the possibility of a concerted mechanism cannot be ruled out. However, considering the similarity of the reacting partners and the activation parameters found in our study and in solution, it appears the same mechanism should apply for both.
    • (1962) J. Am. Chem. Soc. , vol.84 , pp. 892
    • Davis, R.E.1
  • 69
    • 0001631272 scopus 로고
    • Analysis of a great number of solid-state reactions indicated that there is no strong correlation between the chemical specificity and the overall crystallographic order of the final solid phase. See: Gougoutas, J. Z. Pure Appl. Chem. 1971, 27, 305.
    • (1971) Pure Appl. Chem. , vol.27 , pp. 305
    • Gougoutas, J.Z.1
  • 70
    • 0342358408 scopus 로고    scopus 로고
    • note
    • 18 may support the latter suggestion.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.