Binding of dinitrogen to an iron-sulfur-carbon site

Nature

Volumn 526, Issue 7571, 2015, Pages 96-99

  Čorić, Ilija ^a   Mercado, Brandon Q ^a   Bill, Eckhard ^b   Vinyard, David J ^a   Holland, Patrick L ^a  

^a YALE UNIVERSITY   (United States)

^b MAX PLANCK INSTITUTE FOR CHEMICAL ENERGY CONVERSION   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

CARBON; DINITROGEN; IRON; IRON COMPLEX; NITROGEN; NITROGENASE; SULFUR; UNCLASSIFIED DRUG; LIGAND; MOLYBDENUM IRON PROTEIN;

AMMONIA; CARBON; CHEMICAL BINDING; CHEMICAL BONDING; ENZYME ACTIVITY; IRON; MICROBIAL ACTIVITY; MOLYBDENUM; NITROGEN; SULFUR;

ARTICLE; BINDING SITE; CHEMICAL BINDING; ELECTRON; INFRARED SPECTROSCOPY; OXIDATION; PRIORITY JOURNAL; PROTON TRANSPORT; REDUCTION; X RAY DIFFRACTION; CHEMISTRY; METABOLISM;

BINDING SITES; CARBON; ELECTRONS; IRON; LIGANDS; MOLYBDOFERREDOXIN; NITROGEN; NITROGENASE; SULFUR;

EID: 84943148875     PISSN: 00280836     EISSN: 14764687     Source Type: Journal    
DOI: 10.1038/nature15246     Document Type: Article

References (30)

1. Einsle, O. et al. Nitrogenase MoFe-protein at 1.16A resolution: a central ligand in the FeMo-cofactor. Science 297, 1696-1700 (2002).
2. Spatzal, T. et al. Evidence for interstitial carbon in nitrogenase FeMo cofactor. Science 334, 940 (2011).
3. Lancaster, K. M. et al. X-ray emission spectroscopy evidences a central carbon in the nitrogenase iron-molybdenum cofactor. Science 334, 974-977 (2011).
4. Wiig, J. A., Hu, Y., Lee, C. C.&Ribbe,M.W.RadicalSAM-dependent carbon insertion into the nitrogenase M-cluster. Science 337, 1672-1675 (2012).
5. Hoffman, B.M., Lukoyanov, D., Yang, Z.-Y., Dean, D. R. & Seefeldt, L. C. Mechanism of nitrogen fixation by nitrogenase: the next stage. Chem. Rev. 114, 4041-4062 (2014).
6. Seefeldt, L. C., Hoffman, B. M. & Dean, D. R. Mechanism of Mo-dependent nitrogenase. Annu. Rev. Biochem. 78, 701-722 (2009).
7. Spatzal, T., Perez, K. A., Einsle, O., Howard, J. B. & Rees, D. C. Ligand binding to the FeMo-cofactor: structures of CO-bound and reactivated nitrogenase. Science 345, 1620-1623 (2014).
8. Yandulov, D. V. & Schrock, R. R. Catalytic reduction of dinitrogen to ammonia at a single molybdenum center. Science 301, 76-78 (2003).
9. Holland, P. L. Low-coordinate iron complexes as synthetic models of nitrogenase. Can. J. Chem. 83, 296-301 (2005).
10. MacBeth, C. E., Harkins, S. B. & Peters, J. C. Synthesis and characterization of cationic iron complexes supported by the neutral ligands NPi-Pr 3, NArPi-Pr 3, and NSt-Bu3. Can. J. Chem. 83, 332-340 (2005).
11. Dance, I. Ramifications of C-centering rather than N-centering of the active site FeMo-co of the enzyme nitrogenase. Dalton Trans. 41, 4859-4865 (2012).
12. Hinnemann, B.& Nørskov, J. K. Chemical activity of the nitrogenase FeMo cofactor with a central nitrogen ligand: density functional study. J. Am. Chem. Soc. 126, 3920-3927 (2004).
13. George, S. J. et al. EXAFS andNRVS reveal a conformational distortion of the FeMocofactor in the MoFe nitrogenase propargyl alcohol complex. J. Inorg. Biochem. 112, 85-92 (2012).
14. Creutz, S. E. & Peters, J. C. Catalytic reduction of N2 to NH3 by an Fe-N2 complex featuring a C-atom anchor. J. Am. Chem. Soc. 136, 1105-1115 (2014).
15. Anderson, J. S., Rittle, J.& Peters, J. C. Catalytic conversion of nitrogen toammonia by an iron model complex. Nature 501, 84-87 (2013).
16. Kästner, J. & Blöchl, P. E. Ammonia production at the FeMo cofactor of nitrogenase: results from density functional theory. J. Am. Chem. Soc. 129, 2998-3006 (2007).
17. Schimpl, J., Petrilli, H. M. & Blöchl, P. E. Nitrogen binding to the FeMo-cofactor of nitrogenase. J. Am. Chem. Soc. 125, 15772-15778 (2003).
18. Alwaaly, A., Dance, I. & Henderson, R. A. Unexpected explanation for the enigmatic acid-catalysed reactivity of [Fe4S4X4]22 clusters. Chem. Commun. 50, 4799-4802 (2014).
19. Saouma, C. T., Morris, W. D., Darcy, J. W. & Mayer, J. M. Protonation and protoncoupled electron transfer at S-ligated [4Fe-4S] clusters. Chem. Eur. J. 21, 9256-9260 (2015).
20. Lee, S. C., Lo, W. & Holm, R. H. Developments in the biomimetic chemistry of cubane-type and higher nuclearity iron-sulfur clusters. Chem. Rev. 114, 3579-3600 (2014).
21. Ung, G. & Peters, J. C. Low-temperature N2 binding to two-coordinate L2Fe0 enables reductive trapping of L2FeN2 2 and NH3 generation. Angew. Chem. Int. Ed. 54, 532-535 (2015).
22. Rodriguez, M. M., Bill, E., Brennessel, W. W. & Holland, P. L. N2 reduction and hydrogenation toammonia by amolecular iron-potassiumcomplex. Science 334, 780-783 (2011).
23. Hazari, N. Homogeneous iron complexes for the conversion of dinitrogen into ammonia and hydrazine. Chem. Soc. Rev. 39, 4044-4056 (2010).
24. Danopoulos, A. A., Wright, J. A. & Motherwell, W. B. MolecularN2 complexes of iron stabilised byN-heterocyclic 'pincer' dicarbene ligands. Chem. Commun. 784-786 (2005).
25. Takaoka, A., Mankad, N. P. & Peters, J. C. Dinitrogen complexes of sulfur-ligated iron. J. Am. Chem. Soc. 133, 8440-8443 (2011).
26. Bart, S. C., Lobkovsky, E., Bill, E., Wieghardt, K. & Chirik, P. J. Neutral-ligand complexes of bis(imino)pyridine iron: synthesis, structure, and spectroscopy. Inorg. Chem. 46, 7055-7063 (2007).
27. Creutz, S. E. & Peters, J. C. Diiron bridged-thiolate complexes that bind N2 at the FeIIFeII, FeIIFeI, and FeIFeI redox states. J. Am. Chem. Soc. 137, 7310-7313 (2015).
28. Ellison, J. J., Ruhlandt-Senge, K. & Power, P. P. Synthesis and characterization of thiolato complexes with two-coordinate iron(II). Angew. Chem. Int. Edn Engl. 33, 1178-1180 (1994).
29. Suess, D. L. M. & Peters, J. C. H-H and Si-H bond addition to Fe;NNR2 intermediates derived from N2. J. Am. Chem. Soc. 135, 4938-4941 (2013).
30. Moret, M.-E. & Peters, J. C. Terminal iron dinitrogen and iron imide complexes supported by a tris(phosphino)borane ligand. Angew. Chem. Int. Ed. 50, 2063-2067 (2011).