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Volumn 128, Issue 13, 2006, Pages 4348-4355

Mechanism of Pd(OAc)2/DMSO-catalyzed aerobic alcohol oxidation: Mass-transfer-limitation effects and catalyst decomposition pathways

Author keywords

[No Author keywords available]

Indexed keywords

ALCOHOLS; BENZENE; CATALYSTS; DECOMPOSITION; DISSOLUTION; MASS TRANSFER; PALLADIUM; SOLUTIONS; SUBSTRATES;

EID: 33645467565     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja057914b     Document Type: Article
Times cited : (222)

References (63)
  • 1
    • 24944468108 scopus 로고    scopus 로고
    • For recent review articles and accounts, see the following: (a) Stahl, S. S. Science 2005, 309, 1824-1826.
    • (2005) Science , vol.309 , pp. 1824-1826
    • Stahl, S.S.1
  • 16
    • 33645462277 scopus 로고    scopus 로고
    • note
    • 2/DMSO catalyst system in aerobic oxidation reactions. See, for example: (a) Ref If.
  • 48
    • 33645467551 scopus 로고    scopus 로고
    • note
    • 2 (recrystallized from toluene) in DMSO results in rapid disproportionation. In contrast, if hydrogen peroxide is added to a suspension of palladium black obtained from a completed catalytic reaction, disproportionation is slow. These observations suggest that the Pd-catalyzed disproportionation mechanism may proceed via a Pd(II)TPd(IV) cycle.
  • 49
    • 0003059597 scopus 로고
    • Rylander, P. N., Greenfield, H., Eds.; Academic Press: New York
    • For a discussion of mass-transfer-limitation effects in catalysis, see: Roberts, G. W. In Catalysis in Organic Syntheses; Rylander, P. N., Greenfield, H., Eds.; Academic Press: New York, 1976; pp 1-48.
    • (1976) Catalysis in Organic Syntheses , pp. 1-48
    • Roberts, G.W.1
  • 54
    • 0030714094 scopus 로고    scopus 로고
    • For extensive references to this literature, see the following: (a) Watzky, M. A.; Finke, R. G. J. Am. Chem. Soc. 1997, 119, 10382-10400.
    • (1997) J. Am. Chem. Soc. , vol.119 , pp. 10382-10400
    • Watzky, M.A.1    Finke, R.G.2
  • 57
    • 33645462068 scopus 로고    scopus 로고
    • note
    • 2] dependence is therefore explained by invoking a higher-order (>1) dependence of the decomposition rate on [Pd].
  • 58
    • 33645470379 scopus 로고    scopus 로고
    • note
    • 2/pyridine-catalyzed reaction also reveal saturation dependence on [alcohol] (cf. Figure 3B); however, a first-order approximation for the [alcohol] dependence led to a very good exponential fit of the reaction timecourse.
  • 59
    • 33645473695 scopus 로고    scopus 로고
    • note
    • hi).
  • 60
    • 33645473985 scopus 로고    scopus 로고
    • note
    • It might be expected that a different set of rate equations would apply to reactions that exhibit mass-transfer-limitation effects because the rate is formally not dependent on the [alcohol] under these conditions. However, only the initial rate is limited by mass-transfer effects. Analysis of the timecourse data reveals that the reaction rate quickly falls below the mass-transfer limit (i.e., within the first few minutes), and >95% of the data is acquired under conditions that exhibit the typical [alcohol] dependence.
  • 61
    • 4143086010 scopus 로고    scopus 로고
    • This observation underlies our current interest in the effects of the catalyst coordination environment on the rates of palladium(0) oxygenation. See ref 14 and the following: Konnick, M. M.; Guzei. I. A.; Stahl, S. S. J. Am. Chem. Soc. 2004, 126, 10212-10213.
    • (2004) J. Am. Chem. Soc. , vol.126 , pp. 10212-10213
    • Konnick, M.M.1    Guzei, I.A.2    Stahl, S.S.3
  • 62
    • 33645470024 scopus 로고    scopus 로고
    • note
    • Safety is also a critical consideration in these reactions. In many cases, conditions that employ organic solvents with I atm of oxygen pressure fall within the explosive limits. Specific safety assessments generally must be conducted on a case-by-case basis.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.