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Volumn 21, Issue 18, 2002, Pages 3788-3802

Why does the rhodium-catalyzed hydrosilylation of alkenes take place through a modified Chalk-Harrod mechanism? A theoretical study

Author keywords

[No Author keywords available]

Indexed keywords

CATALYSIS; CATALYSTS; CHEMICAL BONDS; PROBABILITY DENSITY FUNCTION;

EID: 0038682383     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om020239j     Document Type: Article
Times cited : (108)

References (68)
  • 2
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    • Wender, I., Pino, P., Eds.; John Wiley & Sons Ltd.; New York
    • (b) Harrod, J. F.; Chalk, A. J. In Organic Synthesis via Metal Carbonyls; Wender, I., Pino, P., Eds.; John Wiley & Sons Ltd.; New York, 1977; Vol. 2, p 673.
    • (1977) Organic Synthesis via Metal Carbonyls , vol.2 , pp. 673
    • Harrod, J.F.1    Chalk, A.J.2
  • 3
    • 0001418043 scopus 로고
    • Patai, S., Rappoport, Z., Eds.; John Wiley & Sons Ltd.: New York
    • (c) Tilley, T. D. In The Chemistry of Organic Silicon Compounds; Patai, S., Rappoport, Z., Eds.; John Wiley & Sons Ltd.: New York, 1989; p 1415.
    • (1989) The Chemistry of Organic Silicon Compounds , pp. 1415
    • Tilley, T.D.1
  • 4
    • 0000829913 scopus 로고
    • Patai, S., Rappoport, Z., Eds.; John Wiley & Sons Ltd.: New York
    • (d) Ojima, I. In The Chemistry of Organic Silicon Compounds; Patai, S., Rappoport, Z., Eds.; John Wiley & Sons Ltd.: New York, 1989; p 1479.
    • (1989) The Chemistry of Organic Silicon Compounds , pp. 1479
    • Ojima, I.1
  • 5
    • 0012364587 scopus 로고
    • Liebeskind, L. S., Ed.; JAI Press Ltd.: London
    • (e) Ohsima, K. In Advances in Metal-Organic Chemistry; Liebeskind, L. S., Ed.; JAI Press Ltd.: London, 1991; Vol. 2, p 101.
    • (1991) Advances in Metal-Organic Chemistry , vol.2 , pp. 101
    • Ohsima, K.1
  • 45
    • 0037687009 scopus 로고    scopus 로고
    • note
    • The MP4(SDQ)/BS-II//HF/BS-I method was employed in the preliminary calculations.
  • 53
    • 0038024975 scopus 로고    scopus 로고
    • note
    • The transition state was not optimized here, since the rotation of the ethyl group would occur very easily.
  • 54
    • 0038024974 scopus 로고    scopus 로고
    • note
    • This slightly negative activation barrier would arise from the fact that the transition state structure is slightly different among the DFT/BS-I, DFT/BS-II, and MP4(SDQ)/BS-II optimizations. However, the absolute value of the negative activation barrier is very small. Hence, the discrepancy would be very small, and therefore, it is reasonably concluded that the true activation barrier is very small and the ethylene insertion into the Rh-H bond can be correctly compared with the other elementary processes.
  • 55
    • 0038363029 scopus 로고    scopus 로고
    • note
    • 3 hybridization than those of the others, which leads to the longer Rh-H distance, and therefore suppresses formation of the Rh-H agostic interaction; actually this angle is 85° in 5c but about 82° in 5a and 5b.
  • 58
    • 0038363026 scopus 로고    scopus 로고
    • note
    • σ orbital of Rh in the product).
  • 59
    • 0038701327 scopus 로고    scopus 로고
    • note
    • a value with the MP4(SDQ) and CCSD(T) methods.
  • 60
    • 0038701329 scopus 로고    scopus 로고
    • note
    • 3.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.