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Partial synthetic models of FeMoco with sulfide and carbyne ligands: Effect of interstitial atom in nitrogenase active site

Le, Linh N. V. and Bailey, Gwendolyn A. and Scott, Anna G. and Agapie, Theodor (2021) Partial synthetic models of FeMoco with sulfide and carbyne ligands: Effect of interstitial atom in nitrogenase active site. Proceedings of the National Academy of Sciences of the United States of America, 118 (49). Art. No. e2109241118. ISSN 0027-8424. PMCID PMC8670491. doi:10.1073/pnas.2109241118. https://resolver.caltech.edu/CaltechAUTHORS:20211203-175255320

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Abstract

Nitrogen-fixing organisms perform dinitrogen reduction to ammonia at an Fe-M (M = Mo, Fe, or V) cofactor (FeMco) of nitrogenase. FeMco displays eight metal centers bridged by sulfides and a carbide having the MFe₇S₈C cluster composition. The role of the carbide ligand, a unique motif in protein active sites, remains poorly understood. Toward addressing how the carbon bridge affects the physical and chemical properties of the cluster, we isolated synthetic models of subsite MFe₃S₃C displaying sulfides and a chelating carbyne ligand. We developed synthetic protocols for structurally related clusters, [Tp*M’Fe₃S₃X]^(n−), where M’ = Mo or W, the bridging ligand X = CR, N, NR, S, and Tp* = Tris(3,5-dimethyl-1-pyrazolyl)hydroborate, to study the effects of the identity of the heterometal and the bridging X group on structure and electrochemistry. While the nature of M’ results in minor changes, the chelating, μ₃-bridging carbyne has a large impact on reduction potentials, being up to 1 V more reducing compared to nonchelating N and S analogs.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1073/pnas.2109241118DOIArticle
https://www.pnas.org/content/suppl/2021/12/01/2109241118.DCSupplementalPublisherSupporting Information
https://www.ccdc.cam.ac.uk/structures/Search?Ccdcid=2084246&DatabaseToSearch=PublishedRelated ItemData
https://www.ccdc.cam.ac.uk/structures/Search?Ccdcid=2081620&DatabaseToSearch=PublishedRelated ItemData
https://www.ccdc.cam.ac.uk/structures/Search?Ccdcid=2084269&DatabaseToSearch=PublishedRelated ItemData
https://www.ccdc.cam.ac.uk/structures/Search?Ccdcid=2081619&DatabaseToSearch=PublishedRelated ItemData
https://www.ccdc.cam.ac.uk/structures/Search?Ccdcid=2081616&DatabaseToSearch=PublishedRelated ItemData
https://www.ccdc.cam.ac.uk/structures/Search?Ccdcid=2084247&DatabaseToSearch=PublishedRelated ItemData
https://www.ccdc.cam.ac.uk/structures/Search?Ccdcid=2081621&DatabaseToSearch=PublishedRelated ItemData
https://www.ccdc.cam.ac.uk/structures/Search?Ccdcid=2081617&DatabaseToSearch=PublishedRelated ItemData
https://www.ccdc.cam.ac.uk/structures/Search?Ccdcid=2081622&DatabaseToSearch=PublishedRelated ItemData
https://www.ccdc.cam.ac.uk/structures/Search?Ccdcid=2084054&DatabaseToSearch=PublishedRelated ItemData
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8670491/PubMed CentralArticle
ORCID:
AuthorORCID
Le, Linh N. V.0000-0003-1451-2675
Bailey, Gwendolyn A.0000-0002-6636-4128
Agapie, Theodor0000-0002-9692-7614
Additional Information:© 2021 National Academy of Sciences. Published under the PNAS license. Edited by Marcetta Y. Darensbourg, Texas A&M University, College Station, TX, and approved October 26, 2021 (received for review May 20, 2021). We are grateful to the NIH (R01-GM102687B to T.A.), Natural Sciences and Engineering Research Council of Canada (G.A.B.), the Resnick Sustainability Institute at Caltech (G.A.B.), and the NSF (Graduate Research Fellowships Program to A.G.S.) for funding. We thank the Beckman Institute and the Dow Next Generation Grant for instrumentation support. Michael Takase, Lawrence Henling, and Manar Shoshani are thanked for assistance with crystallography. Data Availability: Atomic coordinates and structure factors data have been deposited in the Cambridge Structural Database (CSD) of the Cambridge Crystallographic Data Centre (https://www.ccdc.cam.ac.uk/structures/). CSD reference numbers are as follows: 2084246 (1-Mo), 2081620 (2-W), 2084269 (2-Mo), 2081619 (3), 2081616 (4-W), 2084247 (4-Mo), 2081621 (5), 2081617 (6), 2081622 (7), and 2084054 (8). All other study data are included in the article and/or SI Appendix. Author contributions: L.N.V.L., G.A.B., A.G.S., and T.A. designed research; L.N.V.L., G.A.B., and A.G.S. performed research; L.N.V.L., G.A.B., A.G.S., and T.A. analyzed data; L.N.V.L., G.A.B., A.G.S., and T.A. wrote the paper; and T.A. mentored researchers. The authors declare no competing interest. This article is a PNAS Direct Submission. This article contains supporting information online at https://www.pnas.org/lookup/suppl/doi:10.1073/pnas.2109241118/-/DCSupplemental.
Group:Resnick Sustainability Institute
Funders:
Funding AgencyGrant Number
NIHR01-GM102687B
Natural Sciences and Engineering Research Council of Canada (NSERC)UNSPECIFIED
Resnick Sustainability InstituteUNSPECIFIED
NSF Graduate Research FellowshipUNSPECIFIED
Caltech Beckman InstituteUNSPECIFIED
Dow Next Generation Educator FundUNSPECIFIED
Subject Keywords:FeMoco model; nitrogenase; carbide clusters; reduction potential; iron-sulfur clusters
Issue or Number:49
PubMed Central ID:PMC8670491
DOI:10.1073/pnas.2109241118
Record Number:CaltechAUTHORS:20211203-175255320
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20211203-175255320
Official Citation:Partial synthetic models of FeMoco with sulfide and carbyne ligands: Effect of interstitial atom in nitrogenase active site. Linh N. V. Le, Gwendolyn A. Bailey, Anna G. Scott, Theodor Agapie. Proceedings of the National Academy of Sciences Dec 2021, 118 (49) e2109241118; DOI: 10.1073/pnas.2109241118
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:112195
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:03 Dec 2021 18:43
Last Modified:03 Jun 2022 19:00

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