O2 Activation by Bis(imino)pyridine Iron(II)-Thiolate Complexes

被引：87

作者：

Badiei, Yosra M. ^{[1
]}

Siegler, Maxime A. ^{[1
]}

Goldberg, David P. ^{[1
]}

机构：

[1] Johns Hopkins Univ, Dept Chem, Baltimore, MD 21212 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2011年 / 133卷 / 05期

关键词：

MOUSE CYSTEINE DIOXYGENASE; NONHEME IRON(II) COMPLEX; MECHANISTIC IMPLICATIONS; IRON(IV)-OXO COMPLEX; ELECTRONIC-STRUCTURE; THIOLATE COMPLEXES; NITRILE HYDRATASE; ACTIVE-SITE; OXYGENATION; OXIDATION;

D O I：

10.1021/ja109923a

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The new iron(II)-thiolate complexes [((BIP)-B-iPr)Fe-II(SPh)(Cl)] (1) and [((BIP)-B-iPr)Fe-II(SPh)(OTf)] (2) [BIP = bis(imino)pyridine] were prepared as models for cysteine dioxygenase (CDO), which converts Cys to Cys-SO2H at a (His)(3)Fe-II center. Reaction of 1 and 2 with O-2 leads to Fe-oxygenation and S-oxygenation, respectively. For 1 + O-2, the spectroscopic and reactivity data, including O-18 isotope studies, are consistent with an assignment of an iron (IV)-oxo complex, [((BIP)-B-iPr)Fe-IV(O)(Cl)](+) (3), as the product of oxygenation. In contrast, 2 + O-2 results in direct S-oxygenation to give a sulfonato product, PhSO3-. The positioning of the thiolate ligand in 1 versus 2 appears to play a critical role in determining the outcome of O-2 activation. The thiolate ligands in 1 and 2 are essential for O-2 reactivity and exhibit an important influence over the Fe-III/Fe-II redox potential.

引用

页码：1274 / 1277

页数：4

共 45 条

[1] The mechanism of cysteine oxygenation by cysteine dioxygenase enzymes [J].

Aluri, Swathi ;

de Visser, Sam P. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (48) :14846-+

[2] An iron(II) complex with a N3S2 thioether ligand in the generation of an iron(IV)-oxo complex and its reactivity in olefin epoxidation [J].

Annaraj, Jamespandi ;

Kim, Soohee ;

Seo, Mi Sook ;

Lee, Yong-Min ;

Kim, Youngmee ;

Kim, Sung-Jin ;

Choi, Young S. ;

Jang, Ho G. ;

Nam, Wonwoo .

INORGANICA CHIMICA ACTA, 2009, 362 (03) :1031-1034

[3] Electronic structure of bis(imino)pyridine iron dichloride, monochloride, and neutral ligand complexes: A combined structural, spectroscopic, and computational study [J].

Bart, Suzanne C. ;

Chlopek, Krzysztof ;

Bill, Eckhard ;

Bouwkamp, Marco W. ;

Lobkovsky, Emil ;

Neese, Frank ;

Wieghardt, Karl ;

Chirik, Paul J. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (42) :13901-13912

[4] Synthesis of iron(II), manganese(II), cobalt(II) and ruthenium(II) complexes containing tridentate nitrogen ligands and their application in the catalytic oxidation of alkanes [J].

Britovsek, GJP ;

England, J ;

Spitzmesser, SK ;

White, AJP ;

Williams, DJ .

DALTON TRANSACTIONS, 2005, (05) :945-955

[5] Ligand oxidations in high-spin nickel thiolate complexes and zinc analogues [J].

Chohan, BS ;

Shoner, SC ;

Kovacs, JA ;

Maroney, MJ .

INORGANIC CHEMISTRY, 2004, 43 (24) :7726-7734

[6] Why Do Cysteine Dioxygenase Enzymes Contain a 3-His Ligand Motif Rather than a 2His/1Asp Motif Like Most Nonheme Dioxygenases? [J].

de Visser, Sam P. ;

Straganz, Grit D. .

JOURNAL OF PHYSICAL CHEMISTRY A, 2009, 113 (09) :1835-1846

[7] The Three-His Triad in Dke1: Comparisons to the Classical Facial Triad [J].

Diebold, Adrienne R. ;

Neidig, Michael L. ;

Moran, Graham R. ;

Straganz, Grit D. ;

Solomon, Edward I. .

BIOCHEMISTRY, 2010, 49 (32) :6945-6952

[8] 2-Phenoxypyridyl Dinucleating Ligands for Assembly of Diiron(II) Complexes: Efficient Reactivity with O2 To Form (μ-Oxo)diiron(III) Units [J].

Do, Loi H. ;

Lippard, Stephen J. .

INORGANIC CHEMISTRY, 2009, 48 (22) :10708-10719

[9] Oxygenation of thiolates to S-bonded sulfinate in an iron(III) complex related to nitrile hydratase [J].

Galardon, E ;

Giorgi, M ;

Artaud, I .

CHEMICAL COMMUNICATIONS, 2004, (03) :286-287

[10] Spectroscopic and Computational Characterization of Substrate-Bound Mouse Cysteine Dioxygenase: Nature of the Ferrous and Ferric Cysteine Adducts and Mechanistic Implications [J].

Gardner, Jessica D. ;

Pierce, Brad S. ;

Fox, Brian G. ;

Brunold, Thomas C. .

BIOCHEMISTRY, 2010, 49 (29) :6033-6041

← 1 2 3 4 5 →