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Volumn 20, Issue 14, 2001, Pages 3145-3158

Participation of (η3-allyl)ruthenium(II) complexes in C-C bond formation and C-C bond cleavage. A theoretical study

Author keywords

[No Author keywords available]

Indexed keywords

ALLYLRUTHENIUM COMPLEXES; CLEAVAGE; COUPLING REACTIONS;

EID: 0035833279     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om010011g     Document Type: Article
Times cited : (17)

References (122)
  • 1
    • 84942767100 scopus 로고
    • Wilkinson, G., Stone, F. G. A., Abel, E. W., Eds.; Pergamon Press: Oxford, U.K.
    • (a) Trost, B. M.; Verhoeven, T. R. In Comprehensive Organometallic Chemistry; Wilkinson, G., Stone, F. G. A., Abel, E. W., Eds.; Pergamon Press: Oxford, U.K., 1982; Vol. 8, p 799.
    • (1982) Comprehensive Organometallic Chemistry , vol.8 , pp. 799
    • Trost, B.M.1    Verhoeven, T.R.2
  • 97
    • 0011471705 scopus 로고    scopus 로고
    • note
    • The ration of 40/1 leads to the energy difference between endo and exoo forms of about 9 kcal/mol. The present MP4(SDQ)/BS-II//HF/BS-I calculation considerably underestimated the energy difference.
  • 112
    • 0011510780 scopus 로고    scopus 로고
    • note
    • a values for the second transition states TS1b#2 and TS1c#2, respectively. Thus, paths 1b and 1c are more energy-demanding than path 1a.
  • 113
    • 0011455980 scopus 로고    scopus 로고
    • note
    • 4 atom of the allyl moiety. However, this transition state structure is slightly more unstable than TS3a by ca. 2 kcal/mol (MP4(SDQ)/BS-IV//HF/BS-III).
  • 114
    • 0011469334 scopus 로고    scopus 로고
    • note
    • - easily dissociates from the ruthenium(II) center. Thus, we adopted not I3a but I2a for further investigation about coordination of two molecules of formaldehyde.
  • 115
    • 33751044609 scopus 로고
    • and references therein
    • Fukui, K. Acc. Chem. Res. 1981 14, 363 and references therein.
    • (1981) Acc. Chem. Res. , vol.14 , pp. 363
    • Fukui, K.1
  • 118
    • 0011499999 scopus 로고    scopus 로고
    • note
    • Only one difference in electron redistribution between path 1a and path 4 is that formaldehyde of a spectator ligand is positively charged in path 4 but Br is negatively charged in the path 1a. However, both NBO charges change little in the reaction.
  • 121
    • 0011456888 scopus 로고    scopus 로고
    • note
    • 1-allyl moiety is negatively charged in I4 as well(see the Supporting Information).
  • 122
    • 0011424864 scopus 로고    scopus 로고
    • note
    • 22 while the H (hydride) ligand was not involved in the ruthenium(II) complex investigated here. However, it is reasonably expected that meaningful conclusions concerning coexisting ligand such as CO can be presented.


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