CO2 Reduction Catalyzed by Nitrogenase: Pathways to Formate, Carbon Monoxide, and Methane
Abstract
The reduction of N2 to NH3 by Mo-dependent nitrogenase at its active-site metal cluster FeMo-cofactor utilizes reductive elimination (re) of Fe-bound hydrides with obligatory loss of H2 to activate the enzyme for binding/reduction of N2. Earlier work showed that wild type nitrogenase and a nitrogenase having amino acid substitutions in the MoFe protein near FeMo-cofactor can catalytically reduce CO2 by 2 or 8 electrons/protons to carbon monoxide (CO) and methane (CH4) at low rates. Here, it is demonstrated that nitrogenase preferentially reduces CO2 by 2 electrons/protons to formate (HCOO–) at rates >10 times higher than rates of CO2 reduction to yield CO and CH4. Quantum mechanical (QM) calculations on the doubly-reduced FeMo-cofactor with a Fe-bound hydride and S-bound proton (E2(2H) state) favor a direct reaction of CO2 with the hydride (‘direct hydride transfer’ reaction pathway), with facile hydride transfer to CO2 yielding formate. In contrast, a significant barrier is observed for reaction of Fe-bound CO2 with the hydride (‘associative’ reaction pathway), which leads to CO and CH4. Remarkably, in the direct hydride transfer pathway, the Fe-H behaves as a hydridic hydrogen, whereas in the associative pathway it acts as a protic hydrogen. In conclusion, MoFe proteins having amino acid substitutionsmore »
- Authors:
-
- Utah State Univ., Logan, UT (United States)
- Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
- Intel Corp., Hillsboro, OR (United States)
- Northwestern Univ., Evanston, IL (United States)
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Publication Date:
- Research Org.:
- Utah State Univ., Logan, UT (United States). Dept. of Chemistry and Biochemistry
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1466794
- Grant/Contract Number:
- SC0010687
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 55; Journal Issue: 17; Journal ID: ISSN 0020-1669
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; FeS cluster; Mechanism; Calculation; Metalloenzyme
Citation Formats
Khadka, Nimesh, Dean, Dennis R., Smith, Dayle, Hoffman, Brian M., Raugei, Simone, and Seefeldt, Lance C. CO2 Reduction Catalyzed by Nitrogenase: Pathways to Formate, Carbon Monoxide, and Methane. United States: N. p., 2016.
Web. doi:10.1021/acs.inorgchem.6b00388.
Khadka, Nimesh, Dean, Dennis R., Smith, Dayle, Hoffman, Brian M., Raugei, Simone, & Seefeldt, Lance C. CO2 Reduction Catalyzed by Nitrogenase: Pathways to Formate, Carbon Monoxide, and Methane. United States. https://doi.org/10.1021/acs.inorgchem.6b00388
Khadka, Nimesh, Dean, Dennis R., Smith, Dayle, Hoffman, Brian M., Raugei, Simone, and Seefeldt, Lance C. Mon .
"CO2 Reduction Catalyzed by Nitrogenase: Pathways to Formate, Carbon Monoxide, and Methane". United States. https://doi.org/10.1021/acs.inorgchem.6b00388. https://www.osti.gov/servlets/purl/1466794.
@article{osti_1466794,
title = {CO2 Reduction Catalyzed by Nitrogenase: Pathways to Formate, Carbon Monoxide, and Methane},
author = {Khadka, Nimesh and Dean, Dennis R. and Smith, Dayle and Hoffman, Brian M. and Raugei, Simone and Seefeldt, Lance C.},
abstractNote = {The reduction of N2 to NH3 by Mo-dependent nitrogenase at its active-site metal cluster FeMo-cofactor utilizes reductive elimination (re) of Fe-bound hydrides with obligatory loss of H2 to activate the enzyme for binding/reduction of N2. Earlier work showed that wild type nitrogenase and a nitrogenase having amino acid substitutions in the MoFe protein near FeMo-cofactor can catalytically reduce CO2 by 2 or 8 electrons/protons to carbon monoxide (CO) and methane (CH4) at low rates. Here, it is demonstrated that nitrogenase preferentially reduces CO2 by 2 electrons/protons to formate (HCOO–) at rates >10 times higher than rates of CO2 reduction to yield CO and CH4. Quantum mechanical (QM) calculations on the doubly-reduced FeMo-cofactor with a Fe-bound hydride and S-bound proton (E2(2H) state) favor a direct reaction of CO2 with the hydride (‘direct hydride transfer’ reaction pathway), with facile hydride transfer to CO2 yielding formate. In contrast, a significant barrier is observed for reaction of Fe-bound CO2 with the hydride (‘associative’ reaction pathway), which leads to CO and CH4. Remarkably, in the direct hydride transfer pathway, the Fe-H behaves as a hydridic hydrogen, whereas in the associative pathway it acts as a protic hydrogen. In conclusion, MoFe proteins having amino acid substitutions near FeMo-cofactor (α-70Val→Ala, α -195His→Gln) are found to significantly alter the distribution of products between formate and CO/CH4.},
doi = {10.1021/acs.inorgchem.6b00388},
journal = {Inorganic Chemistry},
number = 17,
volume = 55,
place = {United States},
year = {Mon Aug 08 00:00:00 EDT 2016},
month = {Mon Aug 08 00:00:00 EDT 2016}
}
Web of Science
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