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Volumn 125, Issue 36, 2003, Pages 11041-11050

Aromatic vs aliphatic C-H bond activation by rhodium(I) as a function of agostic interactions: Catalytic H/D exchange between olefins and methanol or water

Author keywords

[No Author keywords available]

Indexed keywords

BOND ACIDITY;

EID: 0042232830     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja029197g     Document Type: Article
Times cited : (108)

References (66)
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    • note
    • We performed quantitative analysis of the exchange rate constants in complex 2 in various solvents and at various temperatures (see ref 10). It was found that the constants are representative of a complex process involving solvent dissociation. Our computational results support this conclusion. Thus, the C-H reductive elimination/oxidative addition mechanism in complexes 2 and 4 appears to be difficult to assess by SST quantitative analysis (although in complex 2 rates of various exchange processes can be compared).
  • 23
    • 0000598513 scopus 로고    scopus 로고
    • For recent review on H/D exchange involving C-H activation see: (a) Junk, T.; Catallo, W. J. Chem. Soc. Rev. 1997, 26, 401. See also ref 1b.
    • (1997) J. Chem. Soc. Rev. , vol.26 , pp. 401
    • Junk, T.1    Catallo, W.2
  • 27
    • 0041288651 scopus 로고    scopus 로고
    • note
    • A high-energy process (barrier of 15.8 kcal/mol), involving concerted C-H reductive elimination and MeOH loss to form 5 directly from 7, was also found.
  • 28
    • 0041789200 scopus 로고    scopus 로고
    • note
    • No exchange pathway involving rotation of the Ph ring was found to take place directly form the agostic complex 7.
  • 29
    • 0042290365 scopus 로고    scopus 로고
    • note
    • The value of ΔG‡ for this barrier is probably underestimated due to hydrogen bonding in the TS between the H atom of the dissociated methanol and the O atom of the coordinated methanol.
  • 30
    • 0041288652 scopus 로고    scopus 로고
    • note
    • No analogue of 9 with two coordinated MeOH molecules was found, Repeated attempts to locate this minimum resulted in the convergence to 8.
  • 32
    • 0042791380 scopus 로고    scopus 로고
    • note
    • Natural population analysis (NPA) [ref 45].
  • 33
    • 0042290364 scopus 로고    scopus 로고
    • note
    • A slightly arenium character of 7 is demonstrated by the bond lengths and bond orders alternation in the aromatic ring, although most of the positive charge is still localized on the metal center, similarly to the system reported in ref 8a.
  • 34
    • 0042540974 scopus 로고
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    • Hoffmann, R.1    Saillard, J.Y.2
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    • Hoffmann, R.; Saillard, J. Y. J. Am. Chem. Soc. 1984, 106, 2006. See also: Low, J. J.; Goddard, W. A. J. Am. Chem. Soc. 1986, 108, 6115.
    • (1986) J. Am. Chem. Soc. , vol.108 , pp. 6115
    • Low, J.J.1    Goddard, W.A.2
  • 54
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    • Grotendorst, J., Ed.; John von Neumann Institute for Computing: Jülich, Germany
    • Dolg, M. In Modern Methods and Algorithms of Quantum Chemistry; Grotendorst, J., Ed.; John von Neumann Institute for Computing: Jülich, Germany, 2000; Vol. 1, pp 479-508.
    • (2000) Modern Methods and Algorithms of Quantum Chemistry , vol.1 , pp. 479-508
    • Dolg, M.1
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    • Schaftenaar, G. Molden 3.6, 1999. URL: http://www.cmbi.kun.nl/schaft/molden/molden.html.
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.