A Bispidine Iron(IV)-Oxo Complex in the Entatic State

被引：47
作者：
Comba, Peter [1 ,2 ]
Fukuzumi, Shunichi [3 ,4 ]
Koke, Carsten [1 ,2 ]
Martin, Bodo [1 ,2 ]
Loehr, Anna-Maria [1 ,2 ]
Straub, Johannes [1 ,2 ]
机构：
[1] Heidelberg Univ, Anorganisch Chem Inst, INF 270, D-69120 Heidelberg, Germany
[2] Heidelberg Univ, Interdisziplinares Zentrum Wissensch Rechnen IWR, INF 270, D-69120 Heidelberg, Germany
[3] Ewha Womans Univ, Dept Chem & Nano Sci, Seoul 120750, South Korea
[4] Meijo Univ, Fac Sci & Engn, Nagoya, Aichi 4688502, Japan
来源：
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2016年 / 55卷 / 37期
关键词：
coordination chemistry; density functional calculations; homogeneous catalysis; iron bispidine complexes; redox potentials; MONONUCLEAR NONHEME IRON(IV)-OXO; ELECTRON-TRANSFER PROPERTIES; OXOIRON(IV) COMPLEXES; OXIDATION REACTIONS; 2-STATE REACTIVITY; OXO COMPLEXES; CHEMISTRY; LIGAND; OXYGEN; IRON;
D O I：
10.1002/anie.201605099
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
For a series of Fe-IV=O complexes with tetra- and pentadentate bispidine ligands, the correlation of their redox potentials with reactivity, involving a variety of substrates for alkane hydroxylation (HAT), alkene epoxidation, and phosphine and thioether oxidation (OAT) are reported. The redox potentials span approximately 350mV and the reaction rates over 8 orders of magnitude. From the experimental data and in comparison with published studies it emerges that electron transfer and the driving force are of major importance, and this is also supported by the DFT-based computational analysis. The striking difference of reactivity of two isomeric systems with pentadentate bispidines is found to be due to a destabilization of the S=1 ground state of one of the ferryl isomers, and this is supported by the experimentally determined redox potentials and published stability constants with a series of first-row transition metal ions with these two isomeric ligands.
引用
收藏
页码：11129 / 11133
页数：5
相关论文
共 41 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]   Influence of Ligand Architecture on Oxidation Reactions by High-Valent Nonheme Manganese Oxo Complexes Using Water as a Source of Oxygen [J].
Barman, Prasenjit ;
Vardhaman, Anil Kumar ;
Martin, Bodo ;
Woerner, Svenja J. ;
Sastri, Chivukula V. ;
Comba, Peter .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2015, 54 (07) :2095-2099
[3]   Stability constants: A new twist in transition metal bispidine chemistry [J].
Born, Karin ;
Comba, Peter ;
Ferrari, Rosana ;
Lawrance, Geoffrey A. ;
Wadepohl, Hubert .
INORGANIC CHEMISTRY, 2007, 46 (02) :458-464
[4]   Catalytic epoxidation and 1,2-dihydroxylation of olefins with bispidine-iron(II)/H2O2 systems [J].
Bukowski, Michael R. ;
Comba, Peter ;
Lienke, Achim ;
Limberg, Christian ;
de Laorden, Carlos Lopez ;
Mas-Balleste, Ruben ;
Merz, Michael ;
Que, Lawrence, Jr. .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2006, 45 (21) :3446-3449
[5]   Bispidine ligand effects on iron/hydrogen peroxide chemistry [J].
Bukowski, MR ;
Comba, P ;
Limberg, C ;
Merz, M ;
Que, L ;
Wistuba, T .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2004, 43 (10) :1283-1287
[6]   Evidence for an Alternative to the Oxygen Rebound Mechanism in C-H Bond Activation by Non-Heme FeIVO Complexes [J].
Cho, Kyung-Bin ;
Wu, Xiujuan ;
Lee, Yong-Min ;
Kwon, Yoon Hye ;
Shaik, Sason ;
Nam, Wonwoo .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2012, 134 (50) :20222-20225
[7]   Electrochemical generation of a nonheme oxoiron(IV) complex [J].
Collins, Michael J. ;
Ray, Kallol ;
Que, Lawrence, Jr. .
INORGANIC CHEMISTRY, 2006, 45 (20) :8009-8011
[8]   Bispidine copper(II) compounds: Effects of the rigid ligand backbone [J].
Comba, P ;
Lienke, A .
INORGANIC CHEMISTRY, 2001, 40 (20) :5206-5209
[9]   Modeling of the redox properties of (hexaamine)cobalt(III/II) couples [J].
Comba, P ;
Sickmuller, AF .
INORGANIC CHEMISTRY, 1997, 36 (20) :4500-4507
[10]   Coordination compounds in the entatic state [J].
Comba, P .
COORDINATION CHEMISTRY REVIEWS, 2000, 200 :217-245
12345