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The enzymes also are thought to possess a terminal sulfido ligand which is expected to play a central role in the catalytic mechanism. Here, we investigate the molybdenum-containing formate dehydrogenase FdsDABG from Cupriavidus necator using a combination of Mo K-edge X-ray absorption spectroscopy (XAS), high-energy-resolution fluorescence-detected (HERFD) XAS, extended X-ray absorption fine structure analysis (EXAFS), and density functional theory (DFT) calculations. We observe only subtle spectroscopic changes upon reduction of the oxidized enzyme by formate, suggesting that redox chemistry does not involve the metal; moreover, EXAFS analysis shows no evidence for a terminal sulfido ligand in the oxidized enzyme. DFT calculations support these findings and suggest that the oxidized enzyme possesses a cysteine persulfido structure, which is reduced by cleavage of the S\u2013S bond to form an Mo\u2013SH species, leaving the formal oxidation state of molybdenum unchanged. Collectively, these results suggest that the catalytic reaction of formate dehydrogenases involves ligand-based redox chemistry at a metal center formally reduced to the Mo(IV) state in the oxidized enzyme.<\/jats:p>","DOI":"10.1021\/jacs.6c01488","type":"journal-article","created":{"date-parts":[[2026,6,4]],"date-time":"2026-06-04T10:43:23Z","timestamp":1780569803000},"page":"23742-23751","source":"Crossref","is-referenced-by-count":4,"title":["Ligand-Based\nRedox Chemistry at the Mo-Containing\nActive Site of\n                    <i>Cupriavidus necator<\/i>\n                    Formate\nDehydrogenase"],"prefix":"10.1021","volume":"148","author":[{"given":"Mehrnaz","family":"Zargham","sequence":"first","affiliation":[{"name":"University of Saskatchewan , , , ,","place":["Saskatoon, Saskatchewan, Canada, S7N 5E2"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sheron","family":"Hakopian","sequence":"additional","affiliation":[{"name":"University of California , , , ,","place":["Riverside, California, United States, 92521"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7609-4996","authenticated-orcid":true,"given":"Dimitri","family":"Niks","sequence":"additional","affiliation":[{"name":"University of California , , , ,","place":["Riverside, California, United States, 92521"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Julien J. H.","family":"Cotelesage","sequence":"additional","affiliation":[{"name":"University of Saskatchewan , , , ,","place":["Saskatoon, Saskatchewan, Canada, S7N 5E2"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8117-1933","authenticated-orcid":true,"given":"Dimosthenis","family":"Sokaras","sequence":"additional","affiliation":[{"name":"SLAC National Accelerator Laboratory, Stanford University , , , ,","place":["Menlo Park, California, United States, 94025"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2176-6905","authenticated-orcid":true,"given":"Thomas","family":"Kroll","sequence":"additional","affiliation":[{"name":"SLAC National Accelerator Laboratory, Stanford University , , , ,","place":["Menlo Park, California, United States, 94025"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0936-2994","authenticated-orcid":true,"given":"Ingrid J.","family":"Pickering","sequence":"additional","affiliation":[{"name":"University of Saskatchewan , , , ,","place":["Saskatoon, Saskatchewan, Canada, S7N 5E2"]},{"name":"University of Saskatchewan , , , ,","place":["Saskatoon, Saskatchewan, Canada, S7N 5B3"]},{"name":"University of Saskatchewan , , , ,","place":["Saskatoon, Saskatchewan, Canada, S7N 5C9"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Russ","family":"Hille","sequence":"additional","affiliation":[{"name":"University of California , , , ,","place":["Riverside, California, United States, 92521"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0420-7493","authenticated-orcid":true,"given":"Graham N.","family":"George","sequence":"additional","affiliation":[{"name":"University of Saskatchewan , , , ,","place":["Saskatoon, Saskatchewan, Canada, S7N 5E2"]},{"name":"University of Saskatchewan , , , ,","place":["Saskatoon, Saskatchewan, Canada, S7N 5B3"]},{"name":"University of Saskatchewan , , , ,","place":["Saskatoon, Saskatchewan, Canada, S7N 5C9"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,6,4]]},"reference":[{"key":"2026073023065347400_cit1","doi-asserted-by":"publisher","DOI":"10.1098\/rstb.2012.0258","article-title":"Beating the acetyl coenzyme A-pathway to the origin\nof life","volume":"368","author":"Nitschke","year":"2013","journal-title":"Philos. 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Biotechnol."},{"key":"2026073023065347400_cit5","doi-asserted-by":"publisher","first-page":"1146","DOI":"10.1110\/ps.062741707","article-title":"High-resolution\nstructures of formate\ndehydrogenase from Candida boidinii","volume":"16","author":"Schirwitz","year":"2007","journal-title":"Protein Sci."},{"key":"2026073023065347400_cit6","doi-asserted-by":"publisher","first-page":"3963","DOI":"10.1021\/cr400443z","article-title":"The mononuclear molybdenum enzymes","volume":"114","author":"Hille","year":"2014","journal-title":"Chem. 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Biol."},{"key":"2026073023065347400_cit18","doi-asserted-by":"publisher","DOI":"10.3390\/molecules28041537","article-title":"The mechanism\nof metal-containing formate dehydrogenases revisited: The formation\nof bicarbonate as product intermediate provides evidence for an oxygen\natom transfer mechanism","volume":"28","author":"Kumar","year":"2023","journal-title":"Molecules"},{"key":"2026073023065347400_cit19","doi-asserted-by":"publisher","DOI":"10.1016\/j.jinorgbio.2022.111788","article-title":"The air-inactivation\nof formate dehydrogenase\nFdsDABG from Cupriavidus necator","volume":"231","author":"Hakopian","year":"2022","journal-title":"J. Inorg. Biochem."},{"key":"2026073023065347400_cit20","first-page":"135","volume-title":"X-ray Absorption Spectroscopy","author":"George","year":"2025"},{"key":"2026073023065347400_cit21","first-page":"84","volume-title":"X-ray Absorption Spectroscopy","author":"George","year":"2025"},{"key":"2026073023065347400_cit22","doi-asserted-by":"publisher","first-page":"283","DOI":"10.1107\/S090904950000683X","article-title":"XAS-Collect:\nA computer program for X-ray absorption spectroscopic data acquisition","volume":"7","author":"George","year":"2000","journal-title":"J. Synchrotron Radiat."},{"key":"2026073023065347400_cit23","doi-asserted-by":"publisher","first-page":"1125","DOI":"10.1063\/1.1143112","article-title":"A high-resolution X-ray\nspectrometer for near-edge absorption studies","volume":"63","author":"Strojanoff","year":"1992","journal-title":"Rev. Sci. 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Technol."},{"key":"2026073023065347400_cit27","unstructured":"McMaster, W. H.; Del Grande, N. K.; Mallett, J. H.; Hubbell, J. H.\n          Compilation\nof X-Ray Cross Sections. Lawrence Livermore National Laboratory Report\nUCRL-50174, Sec II, Rev.1. 1969."},{"key":"2026073023065347400_cit28","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevB.44.4146","article-title":"Ab initio\ncurved-wave X-ray-absorption fine structure","volume":"44","author":"de Leon","year":"1991","journal-title":"Phys. Rev. B"},{"key":"2026073023065347400_cit29","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevB.59.948","article-title":"Multiple-scattering X-ray-absorption fine-structure\nDebye-Waller factor calculations","volume":"59","author":"Poiarkova","year":"1999","journal-title":"Phys. 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