{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,2]],"date-time":"2026-10-02T13:00:31Z","timestamp":1790946031172,"version":"4.1.0"},"reference-count":58,"publisher":"American Chemical Society (ACS)","issue":"23","license":[{"start":{"date-parts":[[2026,6,3]],"date-time":"2026-06-03T00:00:00Z","timestamp":1780444800000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-029"},{"start":{"date-parts":[[2026,6,3]],"date-time":"2026-06-03T00:00:00Z","timestamp":1780444800000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-037"},{"start":{"date-parts":[[2026,6,3]],"date-time":"2026-06-03T00:00:00Z","timestamp":1780444800000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-045"}],"funder":[{"DOI":"10.13039\/100000001","name":"National Science Foundation","doi-asserted-by":"publisher","award":["CHE-2153972"],"award-info":[{"award-number":["CHE-2153972"]}],"id":[{"id":"10.13039\/100000001","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100000888","name":"W. M. Keck Foundation","doi-asserted-by":"publisher","award":["NA"],"award-info":[{"award-number":["NA"]}],"id":[{"id":"10.13039\/100000888","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100007185","name":"University of California, Los Angeles","doi-asserted-by":"publisher","award":["NA"],"award-info":[{"award-number":["NA"]}],"id":[{"id":"10.13039\/100007185","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,6,17]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>Metal-mediated hydrogen atom transfer (MHAT) enables versatile radical hydrofunctionalization reactions, yet asymmetric variants, especially for olefin\u2013olefin coupling, remain unknown with small-molecule catalysts. Here we report an enzymatic solution using engineered protoglobins, establishing a biocatalytic platform for asymmetric MHAT-triggered intramolecular cyclization. Directed evolution of a protoglobin furnished a variant that catalyzes 5-exo-trig radical cyclizations to generate 3,4-substituted pyrrolidines in high yields and up to 98:2 e.r. The reaction tolerates diverse donor and acceptor substituents, including esters, amides, nitriles, nitro groups, imines, and ketones. Mechanistic experiments and DFT calculations support a radical pathway with an ultrafast enantiodetermining radical cyclization. These results show that engineered heme proteins can support new-to-nature MHAT chemistry and exert stereocontrol over rapid radical steps, providing a powerful system for asymmetric MHAT reactions.<\/jats:p>","DOI":"10.1021\/jacs.6c01998","type":"journal-article","created":{"date-parts":[[2026,6,3]],"date-time":"2026-06-03T09:20:07Z","timestamp":1780478407000},"page":"23428-23434","source":"Crossref","is-referenced-by-count":2,"title":["Biocatalytic Metal\nHydrogen Atom Transfer for Asymmetric\nOlefin\u2013Olefin Coupling"],"prefix":"10.1021","volume":"148","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-6064-9317","authenticated-orcid":true,"given":"Rajib","family":"Mandal","sequence":"first","affiliation":[{"name":"University of California , , , ,","place":["Los Angeles, California, United States, 90095"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jaicy","family":"Vallapurackal","sequence":"additional","affiliation":[{"name":"University of California , , , ,","place":["Los Angeles, California, United States, 90095"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Aris V.","family":"Rubio","sequence":"additional","affiliation":[{"name":"University of California , , , ,","place":["Los Angeles, California, United States, 90095"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1817-3607","authenticated-orcid":true,"given":"Justin","family":"Bossenbroek","sequence":"additional","affiliation":[{"name":"University of California , , , ,","place":["Los Angeles, California, United States, 90095"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ethan","family":"Poladian","sequence":"additional","affiliation":[{"name":"University of California , , , ,","place":["Los Angeles, California, United States, 90095"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Rami","family":"Halabi","sequence":"additional","affiliation":[{"name":"University of California , , , ,","place":["Los Angeles, California, United States, 90095"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Charles","family":"Skidmore","sequence":"additional","affiliation":[{"name":"University of California , , , ,","place":["Los Angeles, California, United States, 90095"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Gus","family":"Matone","sequence":"additional","affiliation":[{"name":"University of California , , , ,","place":["Los Angeles, California, United States, 90095"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8387-5261","authenticated-orcid":true,"given":"K. N.","family":"Houk","sequence":"additional","affiliation":[{"name":"University of California , , , ,","place":["Los Angeles, California, United States, 90095"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5620-6997","authenticated-orcid":true,"given":"Soumitra V.","family":"Athavale","sequence":"additional","affiliation":[{"name":"University of California , , , ,","place":["Los Angeles, California, United States, 90095"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,6,3]]},"reference":[{"issue":"25","key":"2026073023075508300_cit1","doi-asserted-by":"publisher","first-page":"8335","DOI":"10.1021\/ja00467a045","article-title":"Hydrogenation of.Alpha.-Methylstyrene by Hydridopentacarbonylmanganese\n(I). Evidence for a Free-Radical Mechanism","volume":"99","author":"Sweany","year":"1977","journal-title":"J. Am. Chem. Soc."},{"issue":"4","key":"2026073023075508300_cit2","doi-asserted-by":"publisher","first-page":"575","DOI":"10.1351\/pac198658040575","article-title":"Free Radical\nMechanisms in Organometallic and Bioorganometallic Chemistry","volume":"58","author":"Halpern","year":"1986","journal-title":"Pure Appl. Chem."},{"issue":"13","key":"2026073023075508300_cit3","doi-asserted-by":"publisher","first-page":"4250","DOI":"10.1021\/ja710455c","article-title":"Unusually Weak Metal\u2013Hydrogen\nBonds in HV(CO)4 (P\u2013P) and Their Effectiveness as\nH\u2022 Donors","volume":"130","author":"Choi","year":"2008","journal-title":"J. Am. Chem. Soc."},{"issue":"15","key":"2026073023075508300_cit4","doi-asserted-by":"publisher","first-page":"8912","DOI":"10.1021\/acs.chemrev.6b00334","article-title":"Mn-, Fe-, and Co-Catalyzed\nRadical Hydrofunctionalizations of Olefins","volume":"116","author":"Crossley","year":"2016","journal-title":"Chem. Rev."},{"issue":"15","key":"2026073023075508300_cit5","doi-asserted-by":"publisher","first-page":"8315","DOI":"10.1021\/acs.chemrev.6b00441","article-title":"Introduction: Metal Hydrides","volume":"116","author":"Norton","year":"2016","journal-title":"Chem. Rev."},{"issue":"46","key":"2026073023075508300_cit6","doi-asserted-by":"publisher","first-page":"12401","DOI":"10.1039\/D0SC04112B","article-title":"Catalytic Hydrogen Atom Transfer\nto Alkenes: A Roadmap\nfor Metal Hydrides and Radicals","volume":"11","author":"Shevick","year":"2020","journal-title":"Chem. Sci."},{"key":"2026073023075508300_cit7","doi-asserted-by":"publisher","first-page":"383","DOI":"10.1002\/0471264180.or100.07","article-title":"Hydrofunctionalization\nof Alkenes by Hydrogen-Atom Transfer","volume-title":"Organic\nReactions","author":"Shenvi","year":"2019"},{"issue":"21","key":"2026073023075508300_cit8","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.202401103","article-title":"Recent Advances in Radical Hydrofunctionalization\nof Alkenes and Dienes via Reductive Metal-Hydride Hydrogen Atom Transfer\n(MHAT)","volume":"28","author":"Shen","year":"2025","journal-title":"Eur. J. Org. Chem."},{"issue":"6","key":"2026073023075508300_cit9","doi-asserted-by":"publisher","first-page":"1071","DOI":"10.1246\/cl.1989.1071","article-title":"A New Method\nfor Preparation of Alcohols from Olefins\nwith Molecular Oxygen and Phenylsilane by the Use of Bis(Acetylacetonato)Cobalt(II)","volume":"18","author":"Isayama","year":"1989","journal-title":"Chem. Lett."},{"issue":"1","key":"2026073023075508300_cit10","doi-asserted-by":"publisher","first-page":"17","DOI":"10.1246\/bcsj.68.17","article-title":"Recent Advances in\nAerobic Oxygenation","volume":"68","author":"Mukaiyama","year":"1995","journal-title":"Bull. Chem. Soc. Jpn."},{"issue":"23","key":"2026073023075508300_cit11","doi-asserted-by":"publisher","first-page":"8294","DOI":"10.1021\/ja052164r","article-title":"Cobalt-Catalyzed\nHydroazidation of\nOlefins: Convenient Access to Alkyl Azides","volume":"127","author":"Waser","year":"2005","journal-title":"J. Am. Chem. Soc."},{"issue":"48","key":"2026073023075508300_cit12","doi-asserted-by":"publisher","first-page":"16788","DOI":"10.1021\/ja5105602","article-title":"Simple, Chemoselective,\nCatalytic Olefin Isomerization","volume":"136","author":"Crossley","year":"2014","journal-title":"J. Am. Chem.\nSoc."},{"issue":"4","key":"2026073023075508300_cit13","doi-asserted-by":"publisher","first-page":"1304","DOI":"10.1021\/ja4117632","article-title":"A Practical and Catalytic Reductive\nOlefin Coupling","volume":"136","author":"Lo","year":"2014","journal-title":"J. Am. Chem. Soc."},{"issue":"7531","key":"2026073023075508300_cit14","doi-asserted-by":"publisher","first-page":"343","DOI":"10.1038\/nature14006","article-title":"Functionalized Olefin\nCross-Coupling to Construct Carbon\u2013Carbon Bonds","volume":"516","author":"Lo","year":"2014","journal-title":"Nature"},{"issue":"19","key":"2026073023075508300_cit15","doi-asserted-by":"publisher","first-page":"6884","DOI":"10.1021\/ja502885c","article-title":"A Method\nfor the Selective Hydrogenation of Alkenyl\nHalides to Alkyl Halides","volume":"136","author":"King","year":"2014","journal-title":"J. Am. Chem. Soc."},{"issue":"4","key":"2026073023075508300_cit16","doi-asserted-by":"publisher","first-page":"1300","DOI":"10.1021\/ja412342g","article-title":"Simple,\nChemoselective Hydrogenation with Thermodynamic Stereocontrol","volume":"136","author":"Iwasaki","year":"2014","journal-title":"J. Am. Chem. Soc."},{"issue":"33","key":"2026073023075508300_cit17","doi-asserted-by":"publisher","first-page":"10597","DOI":"10.1021\/jacs.6b05720","article-title":"Catalytic Synthesis\nof Saturated Oxygen Heterocycles by Hydrofunctionalization of Unactivated\nOlefins: Unprotected and Protected Strategies","volume":"138","author":"Shigehisa","year":"2016","journal-title":"J. Am. Chem. Soc."},{"issue":"45","key":"2026073023075508300_cit18","doi-asserted-by":"publisher","first-page":"19316","DOI":"10.1021\/jacs.0c09544","article-title":"Hydrogenation of\nAlkenes via Cooperative Hydrogen Atom\nTransfer","volume":"142","author":"Kattamuri","year":"2020","journal-title":"J. Am. Chem. Soc."},{"issue":"25","key":"2026073023075508300_cit19","doi-asserted-by":"publisher","first-page":"17296","DOI":"10.1021\/jacs.4c04047","article-title":"Fe\/Thiol Cooperative\nHydrogen Atom Transfer Olefin Hydrogenation: Mechanistic Insights\nThat Inform Enantioselective Catalysis","volume":"146","author":"Buzsaki","year":"2024","journal-title":"J. Am.\nChem. Soc."},{"issue":"7","key":"2026073023075508300_cit20","doi-asserted-by":"publisher","first-page":"838","DOI":"10.1038\/s41929-024-01182-9","article-title":"Mimicking Hydrogen-Atom-Transfer-like Reactivity in Copper-Catalysed\nOlefin Hydrofunctionalization","volume":"7","author":"Wang","year":"2024","journal-title":"Nat. Catal"},{"issue":"1","key":"2026073023075508300_cit21","doi-asserted-by":"publisher","first-page":"9397","DOI":"10.1038\/s41467-024-53281-7","article-title":"Shuttle HAT for Mild Alkene Transfer Hydrofunctionalization","volume":"15","author":"Jankins","year":"2024","journal-title":"Nat. Commun."},{"issue":"34","key":"2026073023075508300_cit22","doi-asserted-by":"publisher","first-page":"15478","DOI":"10.1039\/D5SC04274G","article-title":"Merging Carboxylic\nAcids with Metal-Catalyzed Hydrogen Atom Transfer (MHAT) Chemistry via Alkene-Functionalized Redox-Active Esters","volume":"16","author":"Rodri\u0301guez","year":"2025","journal-title":"Chem. Sci."},{"issue":"1","key":"2026073023075508300_cit23","doi-asserted-by":"publisher","first-page":"7230","DOI":"10.1038\/s41467-024-51706-x","article-title":"Iron-Catalyzed\nRadical Markovnikov Hydrohalogenation and Hydroazidation of Alkenes","volume":"15","author":"Elfert","year":"2024","journal-title":"Nat. Commun."},{"issue":"6","key":"2026073023075508300_cit24","doi-asserted-by":"publisher","first-page":"2484","DOI":"10.1021\/jacs.6b13155","article-title":"Fe-Catalyzed\nC\u2013C\nBond Construction from Olefins via Radicals","volume":"139","author":"Lo","year":"2017","journal-title":"J. Am. Chem. Soc."},{"issue":"19","key":"2026073023075508300_cit25","doi-asserted-by":"publisher","first-page":"7709","DOI":"10.1021\/jacs.9b02844","article-title":"Hydroalkylation of Olefins To Form\nQuaternary Carbons","volume":"141","author":"Green","year":"2019","journal-title":"J. Am. Chem. Soc."},{"key":"2026073023075508300_cit26","doi-asserted-by":"publisher","first-page":"e70017","DOI":"10.1002\/anov.70017","article-title":"Radical Retrosynthesis\nof Natural Products Enabled by Iron-Based Reductive Olefin Coupling","volume":"2","author":"Barnes","year":"2026","journal-title":"Angew. Chem. Novit."},{"issue":"32","key":"2026073023075508300_cit27","doi-asserted-by":"publisher","first-page":"28589","DOI":"10.1021\/jacs.5c08224","article-title":"Total Synthesis of (\u2212)-Neocucurbol C Enabled by Pattern Recognition\nand MHAT Cyclization","volume":"147","author":"Zhong","year":"2025","journal-title":"J. Am. Chem. Soc."},{"issue":"44","key":"2026073023075508300_cit28","doi-asserted-by":"publisher","first-page":"17527","DOI":"10.1021\/jacs.9b10645","article-title":"Catalytic Asymmetric Radical\u2013Polar\nCrossover Hydroalkoxylation","volume":"141","author":"Discolo","year":"2019","journal-title":"J. Am. Chem. Soc."},{"issue":"31","key":"2026073023075508300_cit29","doi-asserted-by":"publisher","first-page":"13481","DOI":"10.1021\/jacs.0c05017","article-title":"Catalyst-\nand Silane-Controlled Enantioselective Hydrofunctionalization of Alkenes\nby Cobalt-Catalyzed Hydrogen Atom Transfer and Radical-Polar Crossover","volume":"142","author":"Ebisawa","year":"2020","journal-title":"J. Am. Chem. Soc."},{"issue":"3","key":"2026073023075508300_cit30","doi-asserted-by":"publisher","DOI":"10.1016\/j.checat.2023.100526","article-title":"Cobalt-Catalyzed HAT\nReaction for Asymmetric Hydrofunctionalization\nof Alkenes and Nucleophiles","volume":"3","author":"Zhang","year":"2023","journal-title":"Chem. Catalysis"},{"issue":"24","key":"2026073023075508300_cit31","doi-asserted-by":"publisher","DOI":"10.1126\/sciadv.adv6571","article-title":"Asymmetric Alkyl-Alkyl\nCoupling between Electron-Deficient and Unactivated\nAlkenes to Access \u03b1-Chiral Phosphines by Ni Catalysis","volume":"11","author":"Zou","year":"2025","journal-title":"Sci. Adv."},{"issue":"18","key":"2026073023075508300_cit32","doi-asserted-by":"publisher","first-page":"7473","DOI":"10.1021\/jacs.9b02117","article-title":"Roles of\nIron Complexes in Catalytic Radical Alkene Cross-Coupling: A Computational\nand Mechanistic Study","volume":"141","author":"Kim","year":"2019","journal-title":"J. Am. Chem. Soc."},{"issue":"3\u20134","key":"2026073023075508300_cit33","doi-asserted-by":"publisher","first-page":"445","DOI":"10.1007\/BF03162540","article-title":"Solvent Effect in the Addition of Thetert-Butyl Radical\nto Acrylonitrile","volume":"5","author":"Salikhov","year":"1993","journal-title":"Appl. Magn. Reson."},{"issue":"19","key":"2026073023075508300_cit34","doi-asserted-by":"publisher","first-page":"6960","DOI":"10.1021\/jo982017u","article-title":"Rate Constants for 5-Exo Secondary Alkyl Radical Cyclizations\nonto Hydrazones and Oxime Ethers via Intramolecular Competition Experiments","volume":"64","author":"Tauh","year":"1999","journal-title":"J. Org. Chem."},{"issue":"6777","key":"2026073023075508300_cit35","doi-asserted-by":"publisher","first-page":"1050","DOI":"10.1126\/science.aea4737","article-title":"Biocatalytic, Asymmetric\nRadical\nHydrogenation of Unactivated Alkenes","volume":"390","author":"Vallapurackal","year":"2025","journal-title":"Science"},{"issue":"8076","key":"2026073023075508300_cit36","doi-asserted-by":"publisher","first-page":"381","DOI":"10.1038\/s41586-025-09308-0","article-title":"Repurposing Haemoproteins\nfor Asymmetric Metal-Catalysed H Atom Transfer","volume":"644","author":"Zhang","year":"2025","journal-title":"Nature"},{"issue":"4","key":"2026073023075508300_cit37","doi-asserted-by":"publisher","first-page":"312","DOI":"10.1038\/s41557-020-00633-7","article-title":"Abiotic\nReduction of Ketones with Silanes Catalysed by Carbonic Anhydrase\nthrough an Enzymatic Zinc Hydride","volume":"13","author":"Ji","year":"2021","journal-title":"Nat. Chem."},{"issue":"40","key":"2026073023075508300_cit38","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202407111","article-title":"Carbonic\nAnhydrase Variants Catalyze the Reduction of Dialkyl Ketones with\nHigh Enantioselectivity","volume":"63","author":"Chen","year":"2024","journal-title":"Angew. Chem. Int. Ed"},{"issue":"24","key":"2026073023075508300_cit39","doi-asserted-by":"publisher","first-page":"10257","DOI":"10.1021\/jm501100b","article-title":"Analysis of the Structural Diversity,\nSubstitution Patterns, and Frequency of Nitrogen Heterocycles among\nU.S. FDA Approved Pharmaceuticals: Miniperspective","volume":"57","author":"Vitaku","year":"2014","journal-title":"J. Med. Chem."},{"issue":"17","key":"2026073023075508300_cit40","doi-asserted-by":"publisher","first-page":"7486","DOI":"10.1021\/acs.jmedchem.8b00295","article-title":"De Novo Design, Synthesis, and Biological\nEvaluation of 3,4-Disubstituted Pyrrolidine Sulfonamides as Potent\nand Selective Glycine Transporter 1 Competitive Inhibitors","volume":"61","author":"Wang","year":"2018","journal-title":"J. Med. Chem."},{"issue":"17","key":"2026073023075508300_cit41","doi-asserted-by":"publisher","first-page":"5313","DOI":"10.1016\/j.bmcl.2010.06.126","article-title":"Discovery of a Factor\nXa Inhibitor (3R,4R)-1-(2,2-Difluoro-Ethyl)-Pyrrolidine-3,4-Dicarboxylic\nAcid 3-[(5-Chloro-Pyridin-2-Yl)-Amide] 4-{[2-Fluoro-4-(2-Oxo-2H-Pyridin-1-Yl)-Phenyl]-Amide}\nas a Clinical Candidate","volume":"20","author":"Anselm","year":"2010","journal-title":"Bioorg. Med. Chem.\nLett."},{"key":"2026073023075508300_cit42","doi-asserted-by":"publisher","DOI":"10.1016\/j.ejmech.2020.112148","article-title":"Design, Synthesis, and Pharmacological Evaluation of 4- or 6-Phenyl-Pyrimidine\nDerivatives as Novel and Selective Janus Kinase 3 Inhibitors","volume":"191","author":"Shu","year":"2020","journal-title":"Eur. J. Med. Chem."},{"issue":"5","key":"2026073023075508300_cit43","doi-asserted-by":"publisher","first-page":"34","DOI":"10.1007\/s41061-021-00347-5","article-title":"Pyrrolidine\nin Drug Discovery: A Versatile Scaffold for Novel Biologically Active\nCompounds","volume":"379","author":"Li Petri","year":"2021","journal-title":"Top Curr. Chem. (Z)"},{"issue":"20","key":"2026073023075508300_cit44","doi-asserted-by":"publisher","first-page":"8892","DOI":"10.1021\/jacs.2c02723","article-title":"Biocatalytic Carbene\nTransfer Using Diazirines","volume":"144","author":"Porter","year":"2022","journal-title":"J. Am. Chem. Soc."},{"issue":"37","key":"2026073023075508300_cit45","doi-asserted-by":"publisher","first-page":"20196","DOI":"10.1021\/jacs.3c08053","article-title":"Enzymatic\nNitrogen Incorporation Using Hydroxylamine","volume":"145","author":"Gao","year":"2023","journal-title":"J. Am. Chem. Soc."},{"issue":"4","key":"2026073023075508300_cit46","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202208936","article-title":"Protoglobin-Catalyzed Formation of Cis -Trifluoromethyl-Substituted Cyclopropanes by Carbene\nTransfer","volume":"62","author":"Schaus","year":"2023","journal-title":"Angew. Chem. Int. Ed"},{"issue":"40","key":"2026073023075508300_cit47","doi-asserted-by":"publisher","first-page":"27267","DOI":"10.1021\/jacs.4c09989","article-title":"Biocatalytic Synthesis\nof \u03b1-Amino Esters via\nNitrene C\u2013H Insertion","volume":"146","author":"Alfonzo","year":"2024","journal-title":"J. Am. Chem. Soc."},{"key":"2026073023075508300_cit48","doi-asserted-by":"publisher","first-page":"79","DOI":"10.1016\/B978-0-12-407693-8.00003-0","article-title":"Protoglobin","volume-title":"Advances in Microbial Physiology","author":"Pesce","year":"2013"},{"issue":"1","key":"2026073023075508300_cit49","doi-asserted-by":"publisher","first-page":"2169","DOI":"10.1038\/s41467-019-09751-4","article-title":"Bridging\nthe Gap between Transition Metal- and Bio-Catalysis via Aqueous Micellar\nCatalysis","volume":"10","author":"Cortes-Clerget","year":"2019","journal-title":"Nat. Commun."},{"issue":"2","key":"2026073023075508300_cit50","doi-asserted-by":"publisher","first-page":"785","DOI":"10.1103\/PhysRevB.37.785","article-title":"Development\nof the Colle-Salvetti\nCorrelation-Energy Formula into a Functional of the Electron Density","volume":"37","author":"Lee","year":"1988","journal-title":"Phys. Rev. B"},{"issue":"7","key":"2026073023075508300_cit51","doi-asserted-by":"publisher","first-page":"5648","DOI":"10.1063\/1.464913","article-title":"Density-Functional\nThermochemistry. III. The Role of Exact Exchange","volume":"98","author":"Becke","year":"1993","journal-title":"J. Chem. Phys."},{"issue":"7","key":"2026073023075508300_cit52","doi-asserted-by":"publisher","first-page":"1456","DOI":"10.1002\/jcc.21759","article-title":"Effect of\nthe Damping Function in\nDispersion Corrected Density Functional Theory","volume":"32","author":"Grimme","year":"2011","journal-title":"J. Comput. Chem."},{"issue":"18","key":"2026073023075508300_cit53","doi-asserted-by":"publisher","first-page":"3297","DOI":"10.1039\/b508541a","article-title":"Balanced Basis Sets\nof Split Valence, Triple Zeta Valence\nand Quadruple Zeta Valence Quality for H to Rn: Design and Assessment\nof Accuracy","volume":"7","author":"Weigend","year":"2005","journal-title":"Phys. Chem. Chem. Phys."},{"key":"2026073023075508300_cit54","doi-asserted-by":"publisher","first-page":"165","DOI":"10.1039\/b314768a","article-title":"Spin-Forbidden\nCO Ligand Recombination in Myoglobin","volume":"127","author":"Harvey","year":"2004","journal-title":"Faraday\nDisc."},{"issue":"1","key":"2026073023075508300_cit55","doi-asserted-by":"publisher","first-page":"4502","DOI":"10.1038\/s41467-018-06615-1","article-title":"Ultrafast\nCarbon Monoxide Photolysis and Heme Spin-Crossover in Myoglobin via\nNonadiabatic Quantum Dynamics","volume":"9","author":"Falahati","year":"2018","journal-title":"Nat. Commun."},{"issue":"20","key":"2026073023075508300_cit56","doi-asserted-by":"publisher","first-page":"14666","DOI":"10.1021\/acs.inorgchem.0c02147","article-title":"Intersystem\nCrossing and Triplet\nDynamics in an Iron(II) N-Heterocyclic Carbene Photosensitizer","volume":"59","author":"Zobel","year":"2020","journal-title":"Inorg. Chem."},{"issue":"17","key":"2026073023075508300_cit57","doi-asserted-by":"publisher","first-page":"18383","DOI":"10.1021\/jacs.6c04303","article-title":"Orchestrating Metal-Hydride\nReactivity in Engineered\nMetalloenzymes: Electronic and Electrostatic Determinants of the Reaction\nMechanism","volume":"148","author":"Chatterjee","year":"2026","journal-title":"J. Am. Chem. Soc."},{"issue":"5","key":"2026073023075508300_cit58","doi-asserted-by":"publisher","first-page":"5443","DOI":"10.1021\/jacs.5c19000","article-title":"Enzymatic\nMetal\u2013Hydrogen Atom\nTransfer with a Cobalt Protoporphyrin Cofactor","volume":"148","author":"Masonheimer","year":"2026","journal-title":"J. Am. Chem. Soc."}],"container-title":["Journal of the American\nChemical Society"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/jacs.6c01998","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/jacsat\/article-pdf\/148\/23\/23428\/66271110\/jacs.6c01998.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/jacsat\/article-pdf\/148\/23\/23428\/66271110\/jacs.6c01998.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,7,31]],"date-time":"2026-07-31T03:08:08Z","timestamp":1785467288000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/jacsat\/article\/148\/23\/23428\/5233434\/Biocatalytic-Metal-Hydrogen-Atom-Transfer-for"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,6,3]]},"references-count":58,"journal-issue":{"issue":"23","published-online":{"date-parts":[[2026,6,3]]},"published-print":{"date-parts":[[2026,6,17]]}},"URL":"https:\/\/doi.org\/10.1021\/jacs.6c01998","relation":{"has-preprint":[{"id-type":"doi","id":"10.26434\/chemrxiv.15001215\/v1","asserted-by":"object"}]},"ISSN":["0002-7863","1520-5126"],"issn-type":[{"value":"0002-7863","type":"print"},{"value":"1520-5126","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,6,3]]}}}