Lewis Acid Activation of the Ferrous Heme-NO Fragment toward the N-N Coupling Reaction with NO To Generate N2O

被引：25

作者：

Abucayon, Erwin G. ^{[1
]}

Khade, Rahul L. ^{[2
]}

Powell, Douglas R. ^{[1
]}

Zhang, Yong ^{[2
]}

Richter-Addo, George B. ^{[1
]}

机构：

[1] Univ Oklahoma, Dept Chem & Biochem, Norman, OK 73019 USA

[2] Stevens Inst Technol, Dept Chem & Chem Biol, Hoboken, NJ 07030 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2018年 / 140卷 / 12期

基金：

美国国家卫生研究院; 美国国家科学基金会;

关键词：

NITRIC-OXIDE REDUCTASE; NITROUS-OXIDE; CENTER-DOT; COMPLEXES; PORPHYRIN; INSIGHTS; MODEL; IONS;

D O I：

10.1021/jacs.7b13681

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Bacterial NO reductase (bacNOR) enzymes utilize a heme/non-heme active site to couple two NO molecules to N2O. We show that BF3 coordination to the nitrosyl O-atom in (OEP)Fe(NO) activates it toward N-N bond formation with NO to generate N2O. N-15-isotopic labeling reveals a reversible nitrosyl exchange reaction and follow-up N-O bond cleavage in the N2O formation step. Other Lewis acids (B(C6F5)(3) and K+) also promote the NO coupling reaction with (OEP)Fe(NO). These results, complemented by DFT calculations, provide experimental support for the cis:b(3) pathway in bacNOR

引用

页码：4204 / 4207

页数：4

共 28 条

[1] Synthesis and characterization of alkylammonium hyponitrites and base-stabilized hyponitrous acid salts [J].

Arulsamy, N ;

Bohle, DS ;

Imonigie, JA ;

Sagan, ES .

INORGANIC CHEMISTRY, 1999, 38 (11) :2716-2725

[2] Reduction of nitric oxide in bacterial nitric oxide reductase - a theoretical model study [J].

Blomberg, L. Mattias ;

Blomberg, Margareta R. A. ;

Siegbahn, Per E. M. .

BIOCHIMICA ET BIOPHYSICA ACTA-BIOENERGETICS, 2006, 1757 (04) :240-252

[3] Can Reduction of NO to N2O in Cytochrome c Dependent Nitric Oxide Reductase Proceed through a Trans-Mechanism? [J].

Blomberg, Margareta R. A. .

BIOCHEMISTRY, 2017, 56 (01) :120-131

[4] Improved free energy profile for reduction of NO in cytochrome c dependent nitric oxide reductase (cNOR) [J].

Blomberg, Margareta R. A. ;

Siegbahn, Per E. M. .

JOURNAL OF COMPUTATIONAL CHEMISTRY, 2016, 37 (19) :1810-1818

[5] Recent Advances in Biosynthetic Modeling of Nitric Oxide Reductases and Insights Gained from Nuclear Resonance Vibrational and Other Spectroscopic Studies [J].

Chakraborty, Saumen ;

Reed, Julian ;

Sage, J. Timothy ;

Branagan, Nicole C. ;

Petrik, Igor D. ;

Miner, Kyle D. ;

Hu, Michael Y. ;

Zhao, Jiyong ;

Alp, E. Ercan ;

Lu, Yi .

INORGANIC CHEMISTRY, 2015, 54 (19) :9317-9329

[6] Olefin complexes of low-valent rhenium [J].

Choualeb, Aldjia ;

Blacque, Olivier ;

Schmalle, Helmut W. ;

Fox, Thomas ;

Hiltebrand, Thomas ;

Berke, Heinz .

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2007, (33) :5246-5261

[7] Intermediates Involved in the Two Electron Reduction of NO to N2O by a Functional Synthetic Model of Heme Containing Bacterial NO Reductase [J].

Collman, James P. ;

Dey, Abhishek ;

Yang, Ying ;

Decreau, Richard A. ;

Ohta, Takehiro ;

Solomon, Edward I. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (49) :16498-+

[8] Real Time Monitoring of N2O Emissions from Agricultural Soils using FTIR Spectroscopy [J].

Dubowski, Y. ;

Harush, D. ;

Shaviv, A. ;

Stone, L. ;

Linker, R. .

SOIL SCIENCE SOCIETY OF AMERICA JOURNAL, 2014, 78 (01) :61-69

[9]

Feldmann C, 2000, Z KRISTALLOGR, V215, P343, DOI 10.1524/zkri.2000.215.6.343

[10] Electronic Structure and Biologically Relevant Reactivity of Low-Spin {FeNO}8 Porphyrin Model Complexes: New Insight from a Bis-Picket Fence Porphyrin [J].

Goodrich, Lauren E. ;

Roy, Saikat ;

Alp, E. Ercan ;

Zhao, Jiyong ;

Hu, Michael Y. ;

Lehnert, Nicolai .

INORGANIC CHEMISTRY, 2013, 52 (13) :7766-7780

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