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Volumn 28, Issue 2, 2009, Pages 441-447

Carbonyl-amplified catalyst performance: Balancing stability against activity for five-coordinate ruthenium hydride and hydridocarbonyl catalysts

Author keywords

[No Author keywords available]

Indexed keywords

CATALYSIS; CATALYSTS; HYDROGENATION; OLEFINS; RUTHENIUM;

EID: 61849144288     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om800778h     Document Type: Article
Times cited : (32)

References (73)
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    • Reduction of ROMP polyoctenes was achieved via tandem catalysis at 50-60 °C and as little as 1 atm of H2: see ref 8. Hydrogenation of polynorbornenes, particularly those bearing bulky substituents, is considerably more demanding; see ref 9. Hydrogen pressures of up to 1000 psi can be required for efficient reduction at these moderate temperatures: the high pressures are preferable to use of higher temperatures, which can trigger competitive thermal cross-linking of the unsaturated polymers. Less satisfactory results have been reported using a range of other catalysts (e.g, Wilkinson's catalyst, RhCl(PPh3)3; the Crabtree catalyst, Ir(COD)(PCy 3, py)]PF6, and various supported palladium catalysts, despite their often outstanding performance in reduction of molecular olefins at relatively low H2 pressures. See, for example, ref 9 and: (a) Lee, L.-B. W, Register, R. A. Macromolecules 2005, 38
    • 2 pressures. See, for example, ref 9 and: (a) Lee, L.-B. W.; Register, R. A. Macromolecules 2005, 38, 1216-1222.
  • 12
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    • Dettmer, C. M.; Gray, M. K.; Torkelson, J. M; Nguyen, S. T. Macromolecules 2004, 37, 5504-5512. (c) Lee, B. S.; Mahajan, S.; Clapham, B.; Janda, K. D. J. Org. Chem. 2004, 69, 3319-3329.
    • (b) Dettmer, C. M.; Gray, M. K.; Torkelson, J. M; Nguyen, S. T. Macromolecules 2004, 37, 5504-5512. (c) Lee, B. S.; Mahajan, S.; Clapham, B.; Janda, K. D. J. Org. Chem. 2004, 69, 3319-3329.
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    • Related advances in methodology by others: (a) McLain, S. J.; McCord, E. F.; Arthur, S. D.; Hauptman, E.; Feldman, J.; Nugent, W. A.; Johnson, L. K.; Mecking, S.; Brookhart, M. Proc. PMSE 1997, 76, 246.
    • Related advances in methodology by others: (a) McLain, S. J.; McCord, E. F.; Arthur, S. D.; Hauptman, E.; Feldman, J.; Nugent, W. A.; Johnson, L. K.; Mecking, S.; Brookhart, M. Proc. PMSE 1997, 76, 246.
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    • 3), followed by thermolysis of the resulting Fischer carbenes. See: (a) Louie, J.; Grubbs, R. H. Organometallics 2002, 21, 2153-2164. (b) Arisawa, M.; Terada, Y.; Takahashi, K.; Nakagawa, M.; Nishida, A. J. Org. Chem. 2006, 71, 4255-4261.
    • 3), followed by thermolysis of the resulting Fischer carbenes. See: (a) Louie, J.; Grubbs, R. H. Organometallics 2002, 21, 2153-2164. (b) Arisawa, M.; Terada, Y.; Takahashi, K.; Nakagawa, M.; Nishida, A. J. Org. Chem. 2006, 71, 4255-4261.
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    • 8 The alcohol cosolvent therefore exerts additional favorable effects beyond any arising from formation of 3a: an increase in the dielectric constant of the reaction medium is almost certainly one relevant factor.
    • 8 The alcohol cosolvent therefore exerts additional favorable effects beyond any arising from formation of 3a: an increase in the dielectric constant of the reaction medium is almost certainly one relevant factor.
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    • in dehydrogenative coupling of cyclic amines and alkenes, see: For a study of 2a in olefin silylation, see: a
    • For a study of 2a in olefin silylation, see: (a) Lachaize, S.; Sabo-Etienne, S.; Donnadieu, B.; Chaudret, B. Chem Commun. 2003, 214-215; in dehydrogenative coupling of cyclic amines and alkenes, see:
    • (2003) Chem Commun , pp. 214-215
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    • A Dupont patent also records its use in hydrogenation catalysis
    • (b) Yi, C. S.; Yun, S. Y.; Guzei, I. A. Organometallics 2004, 23, 5392-5395. A Dupont patent also records its use in hydrogenation catalysis:
    • (2004) Organometallics , vol.23 , pp. 5392-5395
    • Yi, C.S.1    Yun, S.Y.2    Guzei, I.A.3
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    • Beatty, R. P.; Paciello, R. A. U.S Patent 5, 554, 778, 1996.
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    • (a) James, B. R. In Computational Organometallic Chemistry; Wilkinson, G., Ed.; Pergamon: New York, 1982; Vol. 8, Chapter 51, and references therein,
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    • Catalyst 2a exhibits a complex dependence on H2 concentration, possibly reflecting the lower activity of its bis (H2) derivative, as reported for related dihydride catalysts: see ref 35. Borowski, A. F, Sabo-Etienne, S, Chaudret, B. J. Mol. Catal. A 2001, 174, 69-79. Hydrogenation is slow at low H2 pressures, however, and use of elevated temperatures to accelerate reaction causes decomposition. This behavior is discussed in more detail in the following sections
    • 2 pressures, however, and use of elevated temperatures to accelerate reaction causes decomposition. This behavior is discussed in more detail in the following sections.
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.