Catalytic Reduction of CN-, CO, and CO2 by Nitrogenase Cofactors in Lanthanide-driven Reactions

Overview

Journal Angew Chem Int Ed Engl

Specialty Chemistry

Date 2014 Nov 26

PMID 25420957

Citations 25

Authors

Chi Chung Lee

Yilin Hu

Markus W Ribbe

Affiliations

Soon will be listed here.

Abstract

Nitrogenase cofactors can be extracted into an organic solvent to catalyze the reduction of cyanide (CN(-)), carbon monoxide (CO), and carbon dioxide (CO2) without using adenosine triphosphate (ATP), when samarium(II) iodide (SmI2) and 2,6-lutidinium triflate (Lut-H) are employed as a reductant and a proton source, respectively. Driven by SmI2, the cofactors catalytically reduce CN(-) or CO to C1-C4 hydrocarbons, and CO2 to CO and C1-C3 hydrocarbons. The C-C coupling from CO2 indicates a unique Fischer-Tropsch-like reaction with an atypical carbonaceous substrate, whereas the catalytic turnover of CN(-), CO, and CO2 by isolated cofactors suggests the possibility to develop nitrogenase-based electrocatalysts for the production of hydrocarbons from these carbon-containing compounds.

Citing Articles

Ammonia synthesis via an engineered nitrogenase assembly pathway in .

Solomon J, Lee C, Liu Y, Duffin C, Ribbe M, Hu Y Nat Catal. 2024; 7(10):1130-1141.

PMID: 39713742 PMC: 11661828. DOI: 10.1038/s41929-024-01229-x.

Photodriven Sm(III)-to-Sm(II) Reduction for Catalytic Applications.

Johansen C, Boyd E, Tarnopol D, Peters J J Am Chem Soc. 2024; 146(37):25456-25461.

PMID: 39226072 PMC: 11421001. DOI: 10.1021/jacs.4c10053.

Reaction Mechanism for CO Reduction by Mo-Nitrogenase Studied by QM/MM.

Jiang H, Ryde U Inorg Chem. 2024; 63(34):15951-15963.

PMID: 39141025 PMC: 11351180. DOI: 10.1021/acs.inorgchem.4c02323.

Catalytic Reduction of Cyanide to Ammonia and Methane at a Mononuclear Fe Site.

Johansen C, Peters J J Am Chem Soc. 2024; 146(8):5343-5354.

PMID: 38361429 PMC: 10910527. DOI: 10.1021/jacs.3c12395.

Highly Activated Terminal Carbon Monoxide Ligand in an Iron-Sulfur Cluster Model of FeMco with Intermediate Local Spin State at Fe.

Le L, Joyce J, Oyala P, DeBeer S, Agapie T J Am Chem Soc. 2024; 146(8):5045-5050.

PMID: 38358932 PMC: 10910499. DOI: 10.1021/jacs.3c12025.

References

Fay A, Blank M, Lee C, Hu Y, Hodgson K, Hedman B . Characterization of isolated nitrogenase FeVco. J Am Chem Soc. 2010; 132(36):12612-8. PMC: 2940275. DOI: 10.1021/ja1019657. View

Lancaster K, Roemelt M, Ettenhuber P, Hu Y, Ribbe M, Neese F . X-ray emission spectroscopy evidences a central carbon in the nitrogenase iron-molybdenum cofactor. Science. 2011; 334(6058):974-7. PMC: 3800678. DOI: 10.1126/science.1206445. View

Lee C, Hu Y, Ribbe M . ATP-independent formation of hydrocarbons catalyzed by isolated nitrogenase cofactors. Angew Chem Int Ed Engl. 2012; 51(8):1947-9. PMC: 3516927. DOI: 10.1002/anie.201108916. View

Spatzal T, Aksoyoglu M, Zhang L, Andrade S, Schleicher E, Weber S . Evidence for interstitial carbon in nitrogenase FeMo cofactor. Science. 2011; 334(6058):940. PMC: 3268367. DOI: 10.1126/science.1214025. View

Lee C, Hu Y, Ribbe M . Vanadium nitrogenase reduces CO. Science. 2010; 329(5992):642. PMC: 3141295. DOI: 10.1126/science.1191455. View

Eady R . Structureminus signFunction Relationships of Alternative Nitrogenases. Chem Rev. 1996; 96(7):3013-3030. DOI: 10.1021/cr950057h. View

Burgess B, Lowe D . Mechanism of Molybdenum Nitrogenase. Chem Rev. 1996; 96(7):2983-3012. DOI: 10.1021/cr950055x. View

Rebelein J, Hu Y, Ribbe M . Differential reduction of CO₂ by molybdenum and vanadium nitrogenases. Angew Chem Int Ed Engl. 2014; 53(43):11543-6. PMC: 4240507. DOI: 10.1002/anie.201406863. View

Shi C, Hansen H, Lausche A, Norskov J . Trends in electrochemical CO2 reduction activity for open and close-packed metal surfaces. Phys Chem Chem Phys. 2014; 16(10):4720-7. DOI: 10.1039/c3cp54822h. View

10.

Wiig J, Hu Y, Lee C, Ribbe M . Radical SAM-dependent carbon insertion into the nitrogenase M-cluster. Science. 2012; 337(6102):1672-5. PMC: 3836454. DOI: 10.1126/science.1224603. View

11.

Hu Y, Fay A, Ribbe M . Identification of a nitrogenase FeMo cofactor precursor on NifEN complex. Proc Natl Acad Sci U S A. 2005; 102(9):3236-41. PMC: 552928. DOI: 10.1073/pnas.0409201102. View

12.

Corbett M, Hu Y, Fay A, Ribbe M, Hedman B, Hodgson K . Structural insights into a protein-bound iron-molybdenum cofactor precursor. Proc Natl Acad Sci U S A. 2006; 103(5):1238-43. PMC: 1360540. DOI: 10.1073/pnas.0507853103. View

13.

Yang Z, Dean D, Seefeldt L . Molybdenum nitrogenase catalyzes the reduction and coupling of CO to form hydrocarbons. J Biol Chem. 2011; 286(22):19417-21. PMC: 3103320. DOI: 10.1074/jbc.M111.229344. View

14.

Heinen W, Lauwers A . Organic sulfur compounds resulting from the interaction of iron sulfide, hydrogen sulfide and carbon dioxide in an anaerobic aqueous environment. Orig Life Evol Biosph. 1996; 26(2):131-50. DOI: 10.1007/BF01809852. View

15.

Schrock R . Nitrogen reduction: Molybdenum does it again. Nat Chem. 2011; 3(2):95-6. DOI: 10.1038/nchem.977. View

16.

Hu Y, Lee C, Ribbe M . Extending the carbon chain: hydrocarbon formation catalyzed by vanadium/molybdenum nitrogenases. Science. 2011; 333(6043):753-5. PMC: 3153399. DOI: 10.1126/science.1206883. View

17.

Lee C, Hu Y, Ribbe M . Unique features of the nitrogenase VFe protein from Azotobacter vinelandii. Proc Natl Acad Sci U S A. 2009; 106(23):9209-14. PMC: 2695066. DOI: 10.1073/pnas.0904408106. View

18.

Yang Z, Moure V, Dean D, Seefeldt L . Carbon dioxide reduction to methane and coupling with acetylene to form propylene catalyzed by remodeled nitrogenase. Proc Natl Acad Sci U S A. 2012; 109(48):19644-8. PMC: 3511747. DOI: 10.1073/pnas.1213159109. View