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Volumn 126, Issue 33, 2004, Pages 10457-10471

Theoretical study of trans-metalation process in palladium-catalyzed borylation of iodobenzene with diboron

Author keywords

[No Author keywords available]

Indexed keywords

BONDING; CATALYSIS; ELECTRONS; IODINE COMPOUNDS; METAL ANALYSIS;

EID: 84962385341     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja040020r     Document Type: Article
Times cited : (152)

References (122)
  • 1
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    • Wilkinson, G., Stone, F. G. A., Abel, E. W., Eds.; Pergamon Press
    • Trost, B. M. In Comprehensive Organometallic Chemistry; Wilkinson, G., Stone, F. G. A., Abel, E. W., Eds.; Pergamon Press. 1982; Vol. 8, 2457.
    • (1982) Comprehensive Organometallic Chemistry , vol.8 , pp. 2457
    • Trost, B.M.1
  • 16
    • 84962386253 scopus 로고
    • (b) Kosugi, M.; Migita, T. Yuki Gosei Kyokaishi (Japanese) 1980, 38, 1142, Chem. Abst. 1981, 95, 81 044d.
    • (1981) Chem. Abst. , vol.95
  • 89
    • 84962342106 scopus 로고    scopus 로고
    • note
    • (a) These two ways to estimate the entropy were adopted in our previous works.28c,39b
  • 108
    • 84962402060 scopus 로고    scopus 로고
    • note
    • 2 because of the smaller steric repulsion. Thus, the Pd-Beg and X-Beg interactions would be overestimated in the present study, to some extent.
  • 109
    • 84962361773 scopus 로고    scopus 로고
    • note
    • 2 forms an adduct with OH-and OR- because these bases are much stronger and much less bulky than pyridine.
  • 114
    • 84962402784 scopus 로고    scopus 로고
    • note
    • (a) Since the dissociative substitution followed by the trans-metalation is less favorable than the associative substitution followed by the transmetalation, as described in the text, the reaction course involving the dissociative substitution is not investigated in detail here. Thus, we roughly estimated the activation barrier by calculating the energy change as a function of the X-Pd-P angle (X = HO, F, or Cl).
  • 115
    • 84962396054 scopus 로고    scopus 로고
    • note
    • (b) Because of the above reason, we did not optimize the transition state of this process.
  • 116
    • 84962451250 scopus 로고    scopus 로고
    • note
    • 3 complexes to real phosphine complexes.
  • 117
    • 84962417381 scopus 로고    scopus 로고
    • note
    • (b) The solvent molecule stabilizes the coordinatively unsaturated intermediate through the coordination. However, the dissociation of phosphine must occur first in the dissociative substitution. Thus, it is likely to consider that the rate-determining step is dissociation of phosphine.
  • 121
    • 84962451246 scopus 로고    scopus 로고
    • note
    • π bonding interaction between the X and Beg groups; the B-O distance is 1.378Å in HO-Beg. 1.368Å in F-Beg, 1.364Å in Cl-Beg, and 1.360Å in I-Beg. These results clearly indicate that the π-bonding interaction between I and Beg groups is very weak.
  • 122
    • 84962423278 scopus 로고    scopus 로고
    • note
    • AcO-Beg bond energy is calculated to be 130.0 kcal/mol with the DFT/BS-II/DFT/BS-I method. This value is smaller than the HO-Beg and F-Beg bond energies but much larger than the Cl-Beg bond energy. Although the Pd-OAc and Pd-(AcO-Beg) bond energies should be considered in the discussion, the large AcO-Beg bond energy suggests that the palladium acetate complex is one of candidates of good catalysts. Actually, the AcO salt was experimentally used in the first report of Ishiyama et al.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.