Spectroscopic capture and reactivity of S=1/2 nickel(III)-oxygen intermediates in the reaction of a NiII-salt with mCPBA

被引：84

作者：

Pfaff, Florian Felix ^{[1
]}

Heims, Florian ^{[1
]}

Kundu, Subrata ^{[1
]}

Mebs, Stefan ^{[1
]}

Ray, Kallol ^{[1
]}

机构：

[1] Humboldt Univ, Dept Chem, Brook Taylor Str 2, D-12489 Berlin, Germany

来源：

CHEMICAL COMMUNICATIONS | 2012年 / 48卷 / 31期

关键词：

SPIN OXOIRON(IV) COMPLEX; COENZYME-M REDUCTASE; C-H; M-CPBA; ALKANE-HYDROXYLATION; DIOXYGEN ACTIVATION; LIGAND; IRON; COPPER; OXYGENATION;

D O I：

10.1039/c2cc30716b

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Ni(III)-intermediates are trapped by EPR and UV/Vis spectroscopy in the reaction of a Ni(II) salt with mCPBA. On the basis of their oxo-transfer and hydrogen-atom abstraction abilities the intermediates are assigned as the elusive terminal Ni(III)-oxo/hydroxo species. The findings suggest that Ni(III)-O(H) moieties are viable reactants in oxidation catalysis.

引用

页码：3730 / 3732

页数：3

共 34 条

[1] Nickel(II) complexes of tripodal 4N ligands as catalysts for alkane oxidation using m-CPBA as oxidant: ligand stereoelectronic effects on catalysis [J].

Balamurugan, Mani ;

Mayilmurugan, Ramasamy ;

Suresh, Eringathodi ;

Palaniandavar, Mallayan .

DALTON TRANSACTIONS, 2011, 40 (37) :9413-9424

[2] A thiolate-ligated nonheme oxoiron(IV) complex relevant to cytochrome P450 [J].

Bukowski, MR ;

Koehntop, KD ;

Stubna, A ;

Bominaar, EL ;

Halfen, JA ;

Münck, E ;

Nam, W ;

Que, L .

SCIENCE, 2005, 310 (5750) :1000-1002

[3] Dioxygen activation by copper, heme and non-heme iron enzymes: comparison of electronic structures and reactivities [J].

Decker, A ;

Solomon, EI .

CURRENT OPINION IN CHEMICAL BIOLOGY, 2005, 9 (02) :152-163

[4] Biochemical and spectroscopic studies of the electronic structure and reactivity of a methyl-ni species formed on methyl-coenzyme M reductase [J].

Dey, Mishtu ;

Telser, Joshua ;

Kunz, Ryan C. ;

Lees, Nicholas S. ;

Ragsdale, Stephen W. ;

Hoffman, Brian M. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (36) :11030-+

[5] Rapid C-H Bond Activation by a Monocopper(III)-Hydroxide Complex [J].

Donoghue, Patrick J. ;

Tehranchi, Jacqui ;

Cramer, Christopher J. ;

Sarangi, Ritimukta ;

Solomon, Edward I. ;

Tolman, William B. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2011, 133 (44) :17602-17605

[6]

Emmons M. T. K., 2007, ACCOUNTS CHEM RES, V40, P618

[7] 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

[8] 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

[9]

Groves J. T., 1995, CYTOCHROME P450 STRU, V1, P3

[10] High-valent iron in chemical and biological oxidations [J].

Groves, John T. .

JOURNAL OF INORGANIC BIOCHEMISTRY, 2006, 100 (04) :434-447

← 1 2 3 4 →