C-H Bond Activation of Methanol and Ethanol by a High-Spin FeIVO Biomimetic Complex

被引:80
作者
Donald, William A. [1 ,2 ]
McKenzie, Christine J. [3 ]
O'Hair, Richard A. J. [1 ,2 ]
机构
[1] Univ Melbourne, Sch Chem, Inst Mol Sci & Biotechnol Bio21, Melbourne, Vic 3010, Australia
[2] Univ Melbourne, ARC Ctr Excellence Free Rad Chem & Biotechnol, Melbourne, Vic 3010, Australia
[3] Univ So Denmark, Dept Chem & Phys, Odense, Denmark
基金
澳大利亚研究理事会;
关键词
alcohols; biomimetic chemistry; C-H activation; gas-phase reactions; non-heme iron complexes; GAS-PHASE OXIDATION; SPECTROSCOPIC CHARACTERIZATION; OXOIRON(IV) COMPLEX; FE-IV=O; OXO; GENERATION; LIGANDS; HEME;
D O I
10.1002/anie.201102146
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
C-H vs O-H vs C-O bond activation? The non-heme complex [(bpg)Fe IVO]+ activates the αC-H bond of primary alcohols in vacuum through H abstraction by the FeO group in the rate-determining step. Although this effect counteracts any enhancement of reactivity that results from increasing the formal oxidation state of Fe, it increases the reaction selectivity. © 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
引用
收藏
页码:8379 / 8383
页数:5
相关论文
共 31 条
[1]   SELECTIVE INTERMOLECULAR CARBON-HYDROGEN BOND ACTIVATION BY SYNTHETIC METAL-COMPLEXES IN HOMOGENEOUS SOLUTION [J].
ARNDTSEN, BA ;
BERGMAN, RG ;
MOBLEY, TA ;
PETERSON, TH .
ACCOUNTS OF CHEMICAL RESEARCH, 1995, 28 (03) :154-162
[2]   ENERGY-ADJUSTED ABINITIO PSEUDOPOTENTIALS FOR THE 1ST-ROW TRANSITION-ELEMENTS [J].
DOLG, M ;
WEDIG, U ;
STOLL, H ;
PREUSS, H .
JOURNAL OF CHEMICAL PHYSICS, 1987, 86 (02) :866-872
[3]   The Crystal Structure of a High-Spin Oxoiron(IV) Complex and Characterization of Its Self-Decay Pathway [J].
England, Jason ;
Guo, Yisong ;
Farquhar, Erik R. ;
Young, Victor G., Jr. ;
Muenck, Eckard ;
Que, Lawrence, Jr. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2010, 132 (25) :8635-8644
[4]   A Synthetic High-Spin Oxoiron(IV) Complex: Generation, Spectroscopic Characterization, and Reactivity [J].
England, Jason ;
Martinho, Marlene ;
Farquhar, Erik R. ;
Frisch, Jonathan R. ;
Bominaar, Emile L. ;
Muenck, Eckard ;
Que, Lawrence, Jr. .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2009, 48 (20) :3622-3626
[5]  
Frisch M. J., 2016, Gaussian 03 Revision B.03
[6]   The biochemistry of methane oxidation [J].
Hakemian, Amanda S. ;
Rosenzweig, Amy C. .
ANNUAL REVIEW OF BIOCHEMISTRY, 2007, 76 :223-241
[7]   Nonheme FeIVO complexes that can oxidize the C-H bonds of cyclohexane at room temperature [J].
Kaizer, J ;
Klinker, EJ ;
Oh, NY ;
Rohde, JU ;
Song, WJ ;
Stubna, A ;
Kim, J ;
Münck, E ;
Nam, W ;
Que, L .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (02) :472-473
[8]  
Klinker E J., 2005, Angew. Chem, V117, P3756
[9]   Structures of nonheme oxoiron(IV) complexes from x-ray crystallography, NMR spectroscopy, and DFT calculations [J].
Klinker, EJ ;
Kaizer, J ;
Brennessel, WW ;
Woodrum, NL ;
Cramer, CJ ;
Que, L .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2005, 44 (24) :3690-3694
[10]   Non-heme Fe(IV)-oxo intermediates [J].
Krebs, Carsten ;
Fujimori, Danica Galonic ;
Walsh, Christopher T. ;
Bollinger, J. Martin, Jr. .
ACCOUNTS OF CHEMICAL RESEARCH, 2007, 40 (07) :484-492