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Volumn 129, Issue 27, 2007, Pages 8487-8499

Activity of rhodium-catalyzed hydroformylation: Added insight and predictions from theory

Author keywords

[No Author keywords available]

Indexed keywords

CATALYTIC CYCLE; MONOSUBSTITUTED RHODIUM-CARBONYL CATALYSTS; MONOSUBSTITUTION;

EID: 34447532254     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja070395n     Document Type: Article
Times cited : (94)

References (127)
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    • Roelen, O. Chemische Verwertungsgesellschaft Oberhausen m.b.H., German Patent DE 849,548 1938/1952; U.S. Patent 2,317066, 1943.
  • 10
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    • van Leeuwen, P. W. N. M, Clever, C, Eds, Kluwer Academic Publishers: Dordrecht, The Netherlands
    • Arnoldy, P. In Rhodium Catalyzed Hydroformylation; van Leeuwen, P. W. N. M., Clever, C., Eds.; Kluwer Academic Publishers: Dordrecht, The Netherlands, 2000.
    • (2000) Rhodium Catalyzed Hydroformylation
    • Arnoldy, P.1
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    • (2004) Gaussian 03, revision , Issue.C.02
    • Frisch, M.J.1
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    • Frenz, B. A.; Ibers, J. A. In Transition Metal Hydrides; Muetterties, E. L., Ed.; Modern theoretical chemistry; Marcel Dekker: New York, 1971.
    • Frenz, B. A.; Ibers, J. A. In Transition Metal Hydrides; Muetterties, E. L., Ed.; Modern theoretical chemistry; Marcel Dekker: New York, 1971.
  • 70
    • 34447579987 scopus 로고    scopus 로고
    • The slight deviation from a formally symmetric structure originates from the fact that the optimization was performed in C1 symmetry; see the Computational Details
    • 1 symmetry; see the Computational Details.
  • 75
    • 34447556744 scopus 로고    scopus 로고
    • 38,37 to reach the precursor, 1.
    • 38,37 to reach the precursor, 1.
  • 76
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    • Van, Leeuwen, P. W. N. M.; Roobeek, Shell, C. F.; Brit. Pat. 2 068 377, 1980; Chem. Abstr. 1984, 101, 191142.
    • Van, Leeuwen, P. W. N. M.; Roobeek, Shell, C. F.; Brit. Pat. 2 068 377, 1980; Chem. Abstr. 1984, 101, 191142.
  • 77
    • 34447574732 scopus 로고    scopus 로고
    • We have not been able to locate reports on recorded catalytic activity of PMe3-modified rhodium catalysts for hydroformylation
    • 3-modified rhodium catalysts for hydroformylation.
  • 78
    • 0003868337 scopus 로고    scopus 로고
    • van Leeuwen, P. W. N. M, Clever, C, Eds, Kluwer Academic Publishers: Dordrecht, The Netherlands
    • Lazzaroni, R.; Settambolo, R.; Caiazzo, A. In Rhodium Catalyzed Hydroformylation; van Leeuwen, P. W. N. M., Clever, C., Eds.; Kluwer Academic Publishers: Dordrecht, The Netherlands, 2000.
    • (2000) Rhodium Catalyzed Hydroformylation
    • Lazzaroni, R.1    Settambolo, R.2    Caiazzo, A.3
  • 90
    • 34447561673 scopus 로고    scopus 로고
    • Energies and structural data reported for the complexes of NHC ligands are in all cases those of the most stable conformers
    • Energies and structural data reported for the complexes of NHC ligands are in all cases those of the most stable conformers.
  • 91
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    • TS4) is thus calculated relative to 6 instead of 7.
    • TS4) is thus calculated relative to 6 instead of 7.
  • 94
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    • For the monosubstituted complexes, the mean value of the three CO stretching frequencies computed for the precursor, 1, has been found to correlate excellently (R2, 0.99) with the χ parameter93 of the phosphorus ligand. The χ parameter for P(OCH2CF3)3 has therefore been predicted by using the stretching frequencies computed for HRh(CO)3P(OCH 2CF3)3 and the linear relationship established between the frequencies in HRh(CO)3L and χL for L, PMe3, PEt3, P(iPr)3, PPh 3, P(OMe)3, and P(OPh)3
    • 3.
  • 95
    • 34447568231 scopus 로고    scopus 로고
    • The correlation coefficient between θ and χ in the set of seven phosphorus ligands is low R2, 0.34, Thus, the predictor variables are to a large extent independent, and the MLR models built thereof do not display collinearity problems
    • 2 = 0.34). Thus, the predictor variables are to a large extent independent, and the MLR models built thereof do not display collinearity problems.
  • 96
    • 34447546621 scopus 로고    scopus 로고
    • Preliminary calculations on disubstituted complexes initiating hydroformylation by CO dissociation from HRh(CO)2L2 show that, for L, P(OMe)3 and PPh3, ΔG ‡TS1 is > 10 and > 20 kJ/mol higher, respectively, than the corresponding barriers quoted for the monosubstituted complexes in Table 2
    • TS1 is > 10 and > 20 kJ/mol higher, respectively, than the corresponding barriers quoted for the monosubstituted complexes in Table 2.
  • 103
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    • Jpn. Kokai Tokkyo Koho, JP 2002231309
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    • Yoshimura, S.1    Nakajima, H.2    Kamino, M.3
  • 104
  • 124
    • 34447564960 scopus 로고    scopus 로고
    • Imidazol-based NHC ligands with electron-withdrawing substituents at the nitrogen atoms have been achieved.125 Metal complexes of tetrazol-based carbenes are difficult to synthesize since the intermediate tetrazolinylidene decomposes in the presence of a base.126,127 However, electron-withdrawing substituents should increase rather than decrease the stability of the tetrazolinylidene and thus facilitate synthesis of metal complexes coordinated by such tetrazol-based carbenes
    • 126,127 However, electron-withdrawing substituents should increase rather than decrease the stability of the tetrazolinylidene and thus facilitate synthesis of metal complexes coordinated by such tetrazol-based carbenes.


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