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Volumn 131, Issue 39, 2009, Pages 13981-13991

Subtle balance of ligand steric effects in stille transmetalation

Author keywords

[No Author keywords available]

Indexed keywords

CATALYTIC CYCLES; COMPUTATIONAL CHEMISTRY; STERIC EFFECT; STERIC PROPERTIES; STILLE REACTIONS; THEORETICAL STUDY; TRANSMETALATION;

EID: 70349629968     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9007134     Document Type: Article
Times cited : (66)

References (80)
  • 19
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    • (a) Farina, V. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon: Oxford, 1995; Vol.12.v
    • (1995) Comprehensive Organometallic Chemistry II
    • Farina, V.1
  • 39
    • 0001455450 scopus 로고    scopus 로고
    • 3)2Pd(Ar)(X) is formed first and then the cis-isomer isomerizes to the thermodynamically more stable trans-isomer (see Scheme 1).
    • 3)2Pd(Ar)(X) is formed first and then the cis-isomer isomerizes to the thermodynamically more stable trans-isomer (see Scheme 1). Casado, A. L.; Espinet, P. Organometallics 1998, 17, 954.
    • (1998) Organometallics , vol.17 , pp. 954
    • Casado, A.L.1    Espinet, P.2
  • 57
  • 62
    • 70349625095 scopus 로고    scopus 로고
    • note
    • - is endergonic by 36.8 kcal/mol supporting the argument that the transmetalation through an open pathway is an unfeasible proposal.
  • 63
    • 70349617962 scopus 로고    scopus 로고
    • note
    • 3)Pd-(Ar)(Br)(THF).
  • 64
    • 0345733884 scopus 로고    scopus 로고
    • The free energy barrier in solution should be a few kcal/mol smaller than in the gas phase because in solution the rotational and translational motions are suppressed. (a)
    • The free energy barrier in solution should be a few kcal/mol smaller than in the gas phase because in solution the rotational and translational motions are suppressed. (a) Tamura, H.; Yamasaki, H.; Sato, H.; Sakaki, S. J. Am. Chem. Soc. 2003, 125, 16114.
    • (2003) J. Am. Chem. Soc. , vol.125 , pp. 16114
    • Tamura, H.1    Yamasaki, H.2    Sato, H.3    Sakaki, S.4
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    • 3743119954 scopus 로고
    • We are aware of the fact that the Ph-vinyl reductive elimination occurs preferentially through four coordinate complexes when L is not a very bulky ligand (see below reference). To simplify the comparison between the energy profiles given in Figures 1-3, we have restricted our analysis solely to the reductive elimination reaction from three coordinate complexes. This choice does not affect the conclusions drawn, because the Ph-vinyl reductive elimination reaction from a Pd(II) complex is very fast
    • We are aware of the fact that the Ph-vinyl reductive elimination occurs preferentially through four coordinate complexes when L is not a very bulky ligand (see below reference). To simplify the comparison between the energy profiles given in Figures 1-3, we have restricted our analysis solely to the reductive elimination reaction from three coordinate complexes. This choice does not affect the conclusions drawn, because the Ph-vinyl reductive elimination reaction from a Pd(II) complex is very fast: Brown, J. M.; Cooley, N. A. Chem. Rev. 1988, 88, 1031.
    • (1988) Chem. Rev. , vol.88 , pp. 1031
    • Brown, J.M.1    Cooley, N.A.2
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    • 70349614917 scopus 로고    scopus 로고
    • note
    • 2 occurs, the product is most likely to be four coordinated.
  • 72
    • 70349623429 scopus 로고    scopus 로고
    • note
    • 3 substitution reaction is highly endergonic.
  • 76
    • 34547093220 scopus 로고    scopus 로고
    • We have recently shown that the contribution of the phosphine-to-Pd σ-donation to the strength of Pd-phosphine bonding in Pd(II) complexes is much more important than of the Pd-to-phosphine π-back bonding (see below reference). It is thus reasonable to expect a positive correlation between the ó-donating ability of phosphines and the Pd-phosphine bond energies
    • We have recently shown that the contribution of the phosphine-to-Pd σ-donation to the strength of Pd-phosphine bonding in Pd(II) complexes is much more important than of the Pd-to-phosphine π-back bonding (see below reference). It is thus reasonable to expect a positive correlation between the ó-donating ability of phosphines and the Pd-phosphine bond energies: Fazaeli, R.; Ariafard, A.; Jamshidi, S.; Tabatabaie, E. S.; Pishro, K. A. J. Organomet. Chem. 2007, 692, 3984.
    • (2007) J. Organomet. Chem. , vol.692 , pp. 3984
    • Fazaeli, R.1    Ariafard, A.2    Jamshidi, S.3    Tabatabaie, E.S.4    Pishro, K.A.5
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    • note
    • 3.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.