Oxidation of Cyclohexane by High-Valent Iron Bispidine Complexes: Tetradentate versus Pentadentate Ligands

被引:75
作者
Comba, Peter [1 ]
Maurer, Martin [1 ]
Vadivelu, Prabha [1 ]
机构
[1] Heidelberg Univ, Inst Anorgan Chem, D-69120 Heidelberg, Germany
关键词
NONHEME OXOIRON(IV) COMPLEXES; DENSITY-FUNCTIONAL THERMOCHEMISTRY; KETOGLUTARATE DIOXYGENASE TAUD; OXYGEN ACTIVATION; FE-IV=O; SPECTROSCOPIC CHARACTERIZATION; METAL-COMPLEXES; EPOXIDATION; INTERMEDIATE; RADICALS;
D O I
10.1021/ic901702s
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The iron-bispidine-catalyzed oxidation of cyclohexane with H2O2, where either a tetradentate or a pentadentate bispidine ligand is coordinated to the iron center, yields up to 35% cyclohexanol and cyclohexanone (alcohol/ketone ratio of up to 4). Product distribution (including O-18 labeling studies), kinetic isotope effects, and the ratio of tertiary/secondary alcohols with adamantane as a substrate (3 degrees/2 degrees) suggest that (i) H abstraction by a ferryl complex is the rate-determining step and that the emerging cyclohexyl radical is short-lived, (ii) there is a parallel reaction involving oxidation by OH radicals, and (iii) there are considerable differences in the reaction pathways between the tetradentate and pentadentate ligand catalyst. These interpretations are fully supported by a DFT-based computational analysis.
引用
收藏
页码:10389 / 10396
页数:8
相关论文
共 60 条
[1]   Electronic structure of bispidine Iron(IV) oxo complexes [J].
Anastasi, Anna E. ;
Comba, Peter ;
McGrady, John ;
Lienke, Achim ;
Rohwer, Heidi .
INORGANIC CHEMISTRY, 2007, 46 (16) :6420-6426
[2]   A MECHANISTIC PROBE FOR OXYGEN ACTIVATION BY METAL-COMPLEXES AND HYDROPEROXIDES AND ITS APPLICATION TO ALKANE FUNCTIONALIZATION BY [FE(III)CL(2)TRIS(2-PYRIDINYLMETHYL)AMINE](+)BF4- [J].
ARENDS, IWCE ;
INGOLD, KU ;
WAYNER, DDM .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1995, 117 (16) :4710-4711
[3]   Biomimetic high-valent non-heme iron oxidants for the cis-dihydroxylation and epoxidation of olefins [J].
Bautz, Jochen ;
Comba, Peter ;
de laorden, Carlos Lopez ;
Menzel, Matthias ;
Rajaraman, Gopalan .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2007, 46 (42) :8067-8070
[4]   Spin-crossover in an iron(III)-bispidine-alkylperoxide system [J].
Bautz, Jochen ;
Comba, Peter ;
Que, Lawrence, Jr. .
INORGANIC CHEMISTRY, 2006, 45 (18) :7077-7082
[5]   Formation of an aqueous oxoiron(IV) complex at pH 2-6 from a nonheme iron(II) complex and H2O2 [J].
Bautz, Jochen ;
Bukowski, Michael R. ;
Kerscher, Marion ;
Stubna, Audria ;
Comba, Peter ;
Lienke, Achim ;
Munck, Eckard ;
Que, Lawrence, Jr. .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2006, 45 (34) :5681-5684
[6]   DENSITY-FUNCTIONAL THERMOCHEMISTRY .1. THE EFFECT OF THE EXCHANGE-ONLY GRADIENT CORRECTION [J].
BECKE, AD .
JOURNAL OF CHEMICAL PHYSICS, 1992, 96 (03) :2155-2160
[7]   DENSITY-FUNCTIONAL THERMOCHEMISTRY .2. THE EFFECT OF THE PERDEW-WANG GENERALIZED-GRADIENT CORRELATION CORRECTION [J].
BECKE, AD .
JOURNAL OF CHEMICAL PHYSICS, 1992, 97 (12) :9173-9177
[8]   DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE [J].
BECKE, AD .
JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) :5648-5652
[9]   Crystal structure of the non-haem iron halogenase SyrB2 in syringomycin biosynthesis [J].
Blasiak, LC ;
Vaillancourt, FH ;
Walsh, CT ;
Drennan, CL .
NATURE, 2006, 440 (7082) :368-371
[10]   Iron coordination chemistry with tetra-, penta- and hexadentate bispidine-type ligands [J].
Börzel, H ;
Comba, P ;
Hagen, KS ;
Lampeka, YD ;
Lienke, A ;
Linti, G ;
Merz, M ;
Pritzkow, H ;
Tsymbal, LV .
INORGANICA CHIMICA ACTA, 2002, 337 :407-419