Metalloporphyrin-catalyzed homogeneous oxidation in supercritical carbon dioxide

被引：61
作者：
Birnbaum, ER [1 ]
Le Lacheur, RM [1 ]
Horton, AC [1 ]
Tumas, W [1 ]
机构：
[1] Univ Calif Los Alamos Natl Lab, Los Alamos Initiat, Chem Sci & Technol Div, Los Alamos, NM 87545 USA
来源：
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL | 1999年 / 139卷 / 01期
关键词：
oxidation; supercritical carbon dioxide; metalloporphyrins;
D O I：
10.1016/S1381-1169(98)00172-1
中图分类号：
O64 [物理化学（理论化学）、化学物理学];
学科分类号：
070304 ; 081704 ;
摘要：
We report results from a study of the reactivity of the halogenated porphyrins tetrakis(pentafluorophenyl)porphyrinato iron(III) chloride [Fe(TFPP)Cl] and beta-octabromo-tetrakis(pentafluorophenyl)porphyrinato iron(III) chloride [Fe(TFPPBr8)Cl] with dioxygen and cyclohexene in supercritical carbon dioxide. A lower limit for the solubility of the iron porphyrins in sc CO2 was determined. Both halogenated metalloporphyrins were active catalysts for oxidation of cyclohexene to epoxide and allylic oxidation products in sc CO2. Ln 12 h at 80 degrees C, up to 350 and 580 turnovers were observed for Fe(TFPP)Cl and Fe(TFPPBr8)Cl, respectively. We have also explored several organic solvent reactions at high temperature and pressure to benchmark relative activity and selectivity. Activity is higher in organic solvent, but accompanied by substantial oxidation of, or reaction with the solvent. Selectivity for epoxidation with Fe(TFPPBr8)Cl is higher in sc CO2 than in organic solvents, with up to 34% cyclohexene oxide produced. (C) 1999 Elsevier Science B.V. All rights reserved.
引用
收藏
页码：11 / 24
页数：14
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  • [1] AALTONEN O, 1991, CHEMTECH, V21, P240
  • [2] HYDROXYLATION OF LINEAR ALKANES CATALYZED BY IRON PORPHYRINS - PARTICULAR EFFICACY AND REGIOSELECTIVITY OF PERHALOGENATED PORPHYRINS
    BARTOLI, JF
    BRIGAUD, O
    BATTIONI, P
    MANSUY, D
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1991, (06) : 440 - 442
  • [3] On the mechanism of catalytic alkene oxidation by molecular oxygen and halogenated iron porphyrins
    Birnbaum, ER
    Grinstaff, MW
    Labinger, JA
    Bercaw, JE
    Gray, HB
    [J]. JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL, 1995, 104 (02) : L119 - L122
  • [4] F-19 NMR-SPECTRA AND STRUCTURES OF HALOGENATED PORPHYRINS
    BIRNBAUM, ER
    HEDGE, JA
    GRINSTAFF, MW
    SCHAEFER, WP
    HENLING, L
    LABINGER, JA
    BERCAW, JE
    GRAY, HB
    [J]. INORGANIC CHEMISTRY, 1995, 34 (14) : 3625 - 3632
  • [5] BOOCK L, 1992, CHEMTECH, V22, P719
  • [6] SPECTROSCOPY OF FLUID PHASES - THE STUDY OF CHEMICAL-REACTIONS AND EQUILIBRIA UP TO HIGH-PRESSURES
    BUBACK, M
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 1991, 30 (06) : 641 - 653
  • [7] ASYMMETRIC CATALYTIC-HYDROGENATION REACTIONS IN SUPERCRITICAL CARBON-DIOXIDE
    BURK, MJ
    FENG, SG
    GROSS, MF
    TUMAS, W
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1995, 117 (31) : 8277 - 8278
  • [8] REACTION OF IRON(III) PORPHYRINS AND IODOSOXYLENE - ACTIVE OXENE COMPLEX OF CYTOCHROME-P-450
    CHANG, CK
    KUO, MS
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1979, 101 (12) : 3413 - 3415
  • [9] DISPERSION POLYMERIZATIONS IN SUPERCRITICAL CARBON-DIOXIDE
    DESIMONE, JM
    MAURY, EE
    MENCELOGLU, YZ
    MCCLAIN, JB
    ROMACK, TJ
    COMBES, JR
    [J]. SCIENCE, 1994, 265 (5170) : 356 - 359
  • [10] SELECTIVE AIR OXIDATION OF LIGHT ALKANES CATALYZED BY ACTIVATED METALLOPORPHYRINS - THE SEARCH FOR A SUPRABIOTIC SYSTEM
    ELLIS, PE
    LYONS, JE
    [J]. COORDINATION CHEMISTRY REVIEWS, 1990, 105 : 181 - 193
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