How do electronegative substituents make metal complexes better catalysts for the oxidation of hydrocarbons by dioxygen?

被引：48

作者：

Bottcher, A ^{[1
]}

Birnbaum, ER ^{[1
]}

Day, MW ^{[1
]}

Gray, HB ^{[1
]}

Grinstaff, MW ^{[1
]}

Labinger, JA ^{[1
]}

机构：

[1] CALTECH, ARTHUR AMOS NOYES LAB CHEM PHYS, PASADENA, CA 91125 USA

来源：

JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL | 1997年 / 117卷 / 1-3期

关键词：

hydrocarbon oxidation; metalloporphyrins; salen complexes;

D O I：

10.1016/S1381-1169(96)00299-3

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：

Modeling studies support a radical-chain autoxidation mechanism for the aerobic oxidation of isobutane catalyzed by halogenated porphyrin iron complexes. A key role of the electronegative halogen substituents is to increase the Fe-III/(II) redox potential and thereby accelerate oxidation of the intermediate t-butyl hydroperoxide by (porph)Fe-III. The electronic structures of electronegatively substituted salen iron complexes have been characterized by several techniques, and related to changes in catalytic activity for oxidation of cyclohexene. The crystal and molecular structure of [Fe((NO2)(4)salen)(H2O)Cl] is reported.

引用

页码：229 / 242

页数：14

共 36 条

[1] On the mechanism of catalytic alkene oxidation by molecular oxygen and halogenated iron porphyrins [J].

Birnbaum, ER ;

Grinstaff, MW ;

Labinger, JA ;

Bercaw, JE ;

Gray, HB .

JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL, 1995, 104 (02) :L119-L122

[2] ELECTRONIC-STRUCTURES OF HALOGENATED RUTHENIUM PORPHYRINS - CRYSTAL-STRUCTURE OF RUTFPPCL8(CO)H2O (TFPPCL8=OCTA-BETA-CHLOROTETRAKIS(PENTAFLUOROPHENYL)PORPHYRIN) [J].

BIRNBAUM, ER ;

SCHAEFER, WP ;

LABINGER, JA ;

BERCAW, JE ;

GRAY, HB .

INORGANIC CHEMISTRY, 1995, 34 (07) :1751-1755

[3] F-19 NMR-SPECTRA AND STRUCTURES OF HALOGENATED PORPHYRINS [J].

BIRNBAUM, ER ;

HEDGE, JA ;

GRINSTAFF, MW ;

SCHAEFER, WP ;

HENLING, L ;

LABINGER, JA ;

BERCAW, JE ;

GRAY, HB .

INORGANIC CHEMISTRY, 1995, 34 (14) :3625-3632

[4]

BOTTCHER A, IN PRESS J MOL CATAL

[5] A COMPARATIVE SYNTHETIC AND STRUCTURAL STUDY OF MU-OXO AND MU-SULFIDO DERIVATIVES OF N,N'-ETHYLENEBIS(ACETYLACETONEIMINATO)IRON(III), INCLUDING THE SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF THE PARENT COMPOUND [J].

CORAZZA, F ;

FLORIANI, C ;

ZEHNDER, M .

JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1987, (04) :709-714

[6]

Cromer D.T., 1974, INT TABLES XRAY CRYS, VIV, P99

[7]

CROMER DT, 1974, INT TABLES XRAY CRYS, V4, P149

[8]

DUCHAMP DJ, 1964, AM CRYSTALLOGR ASS M, V14, P29

[9] SELECTIVE AIR OXIDATION OF LIGHT ALKANES CATALYZED BY ACTIVATED METALLOPORPHYRINS - THE SEARCH FOR A SUPRABIOTIC SYSTEM [J].

ELLIS, PE ;

LYONS, JE .

COORDINATION CHEMISTRY REVIEWS, 1990, 105 :181-193

[10] PREPARATION AND MAGNETIC PROPERTIES OF SOME SCHIFF BASE-IRON(3) HALIDE COMPLEXES [J].

GERLOCH, M ;

LEWIS, J ;

MABBS, FE ;

RICHARDS, A .

JOURNAL OF THE CHEMICAL SOCIETY A -INORGANIC PHYSICAL THEORETICAL, 1968, (01) :112-&

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