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Here, a series of FeIV\u2550O complexes based on a macrocyclic tetracarbene ligand and with different anionic trans-axial ligands (Lax = CF3COO\u2013, tBuS\u2013, AdaS\u2013) has been comprehensively characterized, including X-ray crystallography in two cases, as well as zero-field and applied-field 57Fe Mo\u0308ssbauer spectroscopy, magnetic susceptibility measurements, magnetic circular dichroism (MCD), and helium-tagging infrared photodissociation (IRPD). This establishes a detailed picture of the electronic structures of these ferryl complexes, featuring a well-separated S = 1 ground state, and the influence of the trans-ligand. The confinement to triplet-only pathways in C\u2013H bond activations and comparison with the parent FeIV\u2550O complex (Lax = MeCN) allow uncovering trends in hydrogen atom abstraction (HAA) ability without perturbations from different extents of two-state reactivity (TSR). Kinetic studies on HAA for C\u2013H substrates with BDEs up to 78 kcal mol\u20131 show relatively minor effects of the axial ligands, with rates following an electrophilic trend in the order Lax = MeCN &amp;gt; CF3COO\u2013 \u2248 RS\u2013. This contrasts the antielectrophilic trend found for a related series of tetramethylcyclam (TMC)-based FeIV\u2550O complexes for which TSR is dominant. For the present systems, temperature-dependent KIEs, in combination with computations at the DFT and ab initio levels of theory, suggest a semiclassical model with modest tunneling contributions that are most pronounced in the case of a strongly donating trans-thiolate. This study thus provides a combined experimental and computational basis for understanding intrinsic axial ligand effects and the effect of a trans-axial thiolate in S = 1 ferryl intermediates.<\/jats:p>","DOI":"10.1021\/jacsau.6c00781","type":"journal-article","created":{"date-parts":[[2026,9,14]],"date-time":"2026-09-14T17:01:32Z","timestamp":1789405292000},"page":"5130-5144","source":"Crossref","is-referenced-by-count":0,"title":["Axial Ligand Effects\non Electronic Structures and\nH-Atom Abstraction by Oxidoiron(IV) Complexes Featuring Triplet-Only\nReactivity"],"prefix":"10.1021","volume":"6","author":[{"given":"Isabelle","family":"Becker","sequence":"first","affiliation":[{"name":"University of Go\u0308ttingen , , Tammannstra\u00dfe 4 , ,","place":["Go\u0308ttingen, Germany, 37077"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Massimiliano","family":"Morganti","sequence":"additional","affiliation":[{"name":"University of Go\u0308ttingen , , Tammannstra\u00dfe 4 , ,","place":["Go\u0308ttingen, Germany, 37077"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1245-0618","authenticated-orcid":true,"given":"Haowei","family":"Chen","sequence":"additional","affiliation":[{"name":"Max-Planck-Institut fu\u0308r Kohlenforschung , ,","place":["Mu\u0308lheim an der Ruhr, Germany, 45470"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Akhil","family":"Bhardwaj","sequence":"additional","affiliation":[{"name":"Indian Institute of Technology Mandi , , Kamand , , ,","place":["Mandi, Himachal Pradesh, India, 175075"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Pilar","family":"Bologna","sequence":"additional","affiliation":[{"name":"University of Go\u0308ttingen , , Tammannstra\u00dfe 4 , ,","place":["Go\u0308ttingen, Germany, 37077"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Guilherme","family":"Tripodi","sequence":"additional","affiliation":[{"name":"Radboud University , , Heyendaalseweg 135 , ,","place":["Nijmegen, Netherlands, 6525"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Serhiy","family":"Demeshko","sequence":"additional","affiliation":[{"name":"University of Go\u0308ttingen , , Tammannstra\u00dfe 4 , ,","place":["Go\u0308ttingen, Germany, 37077"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2864-2449","authenticated-orcid":true,"given":"Sebastian","family":"Dechert","sequence":"additional","affiliation":[{"name":"University of Go\u0308ttingen , , Tammannstra\u00dfe 4 , ,","place":["Go\u0308ttingen, Germany, 37077"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5144-0688","authenticated-orcid":true,"given":"Jana","family":"Roithova\u0301","sequence":"additional","affiliation":[{"name":"Radboud University , , Heyendaalseweg 135 , ,","place":["Nijmegen, Netherlands, 6525"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4691-0547","authenticated-orcid":true,"given":"Frank","family":"Neese","sequence":"additional","affiliation":[{"name":"Max-Planck-Institut fu\u0308r Kohlenforschung , ,","place":["Mu\u0308lheim an der Ruhr, Germany, 45470"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9026-5974","authenticated-orcid":true,"given":"Bhaskar","family":"Mondal","sequence":"additional","affiliation":[{"name":"Indian Institute of Technology Mandi , , Kamand , , ,","place":["Mandi, Himachal Pradesh, India, 175075"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9747-1412","authenticated-orcid":true,"given":"Shengfa","family":"Ye","sequence":"additional","affiliation":[{"name":"Sun Yat-Sen University , , ,","place":["Guangzhou, P.R. China, 510275"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8613-7862","authenticated-orcid":true,"given":"Franc","family":"Meyer","sequence":"additional","affiliation":[{"name":"University of Go\u0308ttingen , , Tammannstra\u00dfe 4 , ,","place":["Go\u0308ttingen, Germany, 37077"]},{"name":"University of Go\u0308ttingen , , Tammannstr. 6 , ,","place":["Go\u0308ttingen, Germany, 37077"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,9,14]]},"reference":[{"issue":"4","key":"2026092808082686100_cit1a","doi-asserted-by":"publisher","first-page":"434","DOI":"10.1016\/j.jinorgbio.2006.01.012","article-title":"High-valent\niron in chemical and biological oxidations","volume":"100","author":"Groves","year":"2006","journal-title":"J. Inorg. 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Biol."},{"key":"2026092808082686100_cit6a","doi-asserted-by":"publisher","first-page":"10039","DOI":"10.1002\/chem.200901238","article-title":"Enhanced Reactivities\nof Iron(IV)-Oxo Porphyrin \u03c0-Cation Radicals in Oxygenation Reactions\nby Electron-Donating Axial Ligands","volume":"15","author":"Kang","year":"2009","journal-title":"Chem. Eur.\nJ."},{"issue":"13","key":"2026092808082686100_cit6b","doi-asserted-by":"publisher","first-page":"7296","DOI":"10.1021\/ic3006597","article-title":"Effect of the Axial\nLigand on the Reactivity of the Oxoiron(IV) Porphyrin \u03c0-Cation\nRadical Complex: Higher Stabilization of the Product State Relative\nto the Reactant State","volume":"51","author":"Takahashi","year":"2012","journal-title":"Inorg. 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Rev."},{"issue":"4","key":"2026092808082686100_cit7b","doi-asserted-by":"publisher","first-page":"1146","DOI":"10.1021\/ar400258p","article-title":"Tuning Reactivity and\nMechanism in Oxidation Reactions by Mononuclear Nonheme Iron(IV)-Oxo\nComplexes","volume":"47","author":"Nam","year":"2014","journal-title":"Acc. Chem. Res."},{"issue":"8","key":"2026092808082686100_cit7c","doi-asserted-by":"publisher","first-page":"2415","DOI":"10.1021\/acs.accounts.5b00218","article-title":"Synthetic Mononuclear Nonheme Iron\u2013Oxygen Intermediates","volume":"48","author":"Nam","year":"2015","journal-title":"Acc. Chem. Res."},{"issue":"9","key":"2026092808082686100_cit7d","doi-asserted-by":"publisher","first-page":"2612","DOI":"10.1021\/acs.accounts.5b00053","article-title":"Bioinspired Nonheme Iron Catalysts\nfor C\u2013H and C\u2550C Bond Oxidation: Insights into the Nature\nof the Metal-Based Oxidants","volume":"48","author":"Oloo","year":"2015","journal-title":"Acc. Chem. Res."},{"key":"2026092808082686100_cit8a","doi-asserted-by":"publisher","first-page":"10","DOI":"10.4019\/bjscc.67.10","article-title":"The Amazing High-Valent\nNonheme Iron-Oxo Landscape","volume":"67","author":"Que","year":"2016","journal-title":"Bull. Jpn. Soc.\nCoord. Chem."},{"key":"2026092808082686100_cit8b","doi-asserted-by":"publisher","first-page":"412","DOI":"10.1016\/B978-0-08-102688-5.00108-2","article-title":"Synthetic Nonheme High-Valent Iron-Oxo Complexes Structures and Oxidative\nFunction","volume-title":"Comprehensive Coordination Chemistry\nIII","author":"Abelson","year":"2021"},{"issue":"1","key":"2026092808082686100_cit9a","doi-asserted-by":"publisher","first-page":"19","DOI":"10.1038\/nchem.943","article-title":"Exchange-enhanced\nreactivity in bond activation by metal\u2013oxo enzymes and synthetic\nreagents","volume":"3","author":"Shaik","year":"2011","journal-title":"Nat. Chem."},{"issue":"1","key":"2026092808082686100_cit9b","doi-asserted-by":"publisher","first-page":"13","DOI":"10.1021\/acscentsci.8b00698","article-title":"Heme and Nonheme High-Valent\nIron and Manganese Oxo Cores in Biological and Abiological Oxidation\nReactions","volume":"5","author":"Guo","year":"2019","journal-title":"ACS Cent. Sci."},{"issue":"1","key":"2026092808082686100_cit9c","doi-asserted-by":"publisher","first-page":"720","DOI":"10.1038\/ncomms1718","article-title":"The biology and chemistry\nof high-valent iron\u2013oxo and iron\u2013nitrido complexes","volume":"3","author":"Hohenberger","year":"2012","journal-title":"Nat. Commun."},{"issue":"7","key":"2026092808082686100_cit9d","doi-asserted-by":"publisher","first-page":"532","DOI":"10.1021\/ar600042c","article-title":"Reactivity of High-Valent Iron\u2013Oxo\nSpecies in Enzymes and Synthetic Reagents: A Tale of Many States","volume":"40","author":"Shaik","year":"2007","journal-title":"Acc. Chem. Res."},{"key":"2026092808082686100_cit10a","doi-asserted-by":"publisher","first-page":"763","DOI":"10.1002\/ijch.201600028","article-title":"High-Valent Iron-Oxo and -Nitrido Complexes: Bonding and Reactivity","volume":"56","author":"Mondal","year":"2016","journal-title":"Isr. J. Chem."},{"issue":"2","key":"2026092808082686100_cit10b","doi-asserted-by":"publisher","first-page":"209","DOI":"10.1021\/acs.accounts.5c00655","article-title":"Electronic Structure Contributions\nto the Reactivity of Mononuclear FeIV-Oxo Intermediates","volume":"59","author":"Braun","year":"2026","journal-title":"Acc. Chem. Res."},{"key":"2026092808082686100_cit11","doi-asserted-by":"publisher","first-page":"893","DOI":"10.1002\/cplu.201900178","article-title":"Theoretical\nIdentification of the Factors Governing the Reactivity of C\u2013H\nBond Activation by Non-Heme Iron(IV)-Oxo Complexes","volume":"84","author":"Roy","year":"2019","journal-title":"ChemPlusChem"},{"key":"2026092808082686100_cit12","doi-asserted-by":"publisher","first-page":"938","DOI":"10.1002\/ijch.202000002","article-title":"Two-State\nReactivity: Personal Recounting of its Conception and Future Prospects","volume":"60","author":"Shaik","year":"2020","journal-title":"Isr. J. Chem."},{"issue":"49","key":"2026092808082686100_cit13","doi-asserted-by":"publisher","first-page":"19181","DOI":"10.1073\/pnas.0709471104","article-title":"Axial ligand tuning of a nonheme\niron(IV)\u2013oxo unit for hydrogen atom abstraction","volume":"104","author":"Sastri","year":"2007","journal-title":"Proc. Natl. Acad. Sci. U. S. A."},{"issue":"5609","key":"2026092808082686100_cit14","doi-asserted-by":"publisher","first-page":"1037","DOI":"10.1126\/science.299.5609.1037","article-title":"Crystallographic and Spectroscopic Characterization\nof a Nonheme Fe(IV)O Complex","volume":"299","author":"Rohde","year":"2003","journal-title":"Science"},{"issue":"15","key":"2026092808082686100_cit15","doi-asserted-by":"publisher","first-page":"2255","DOI":"10.1002\/anie.200462631","article-title":"Axial Coordination of Carboxylate\nActivates the Non-heme FeIV-O Unit","volume":"44","author":"Rohde","year":"2005","journal-title":"Angew. Chem., Int. Ed."},{"issue":"36","key":"2026092808082686100_cit16","doi-asserted-by":"publisher","first-page":"12494","DOI":"10.1021\/ja0540573","article-title":"Axial Ligand Substituted\nNonheme FeIVO Complexes: Observation of Near-UV LMCT Bands\nand FeO Raman Vibrations","volume":"127","author":"Sastri","year":"2005","journal-title":"J. Am. Chem. Soc."},{"issue":"5750","key":"2026092808082686100_cit17","doi-asserted-by":"publisher","first-page":"1000","DOI":"10.1126\/science.1119092","article-title":"A Thiolate-Ligated\nNonheme Oxoiron(IV) Complex Relevant to Cytochrome P450","volume":"310","author":"Bukowski","year":"2005","journal-title":"Science"},{"issue":"6","key":"2026092808082686100_cit18","doi-asserted-by":"publisher","first-page":"1740","DOI":"10.1002\/chem.200701739","article-title":"A Two-State\nReactivity Rationale for Counterintuitive Axial Ligand Effects on\nthe CH Activation Reactivity of Nonheme FeIV\u2550O Oxidants","volume":"14","author":"Hirao","year":"2008","journal-title":"Chem. Eur. J."},{"key":"2026092808082686100_cit19","doi-asserted-by":"publisher","first-page":"3356","DOI":"10.1002\/anie.200705880","article-title":"Experiment and Theory Reveal the Fundamental Difference between Two-State\nand Single-State Reactivity Patterns in Nonheme FeIV\u2550O\nversus RuIV\u2550O Oxidants","volume":"47","author":"Dhuri","year":"2008","journal-title":"Angew.\nChem., Int. Ed."},{"key":"2026092808082686100_cit20","doi-asserted-by":"publisher","first-page":"722","DOI":"10.1021\/ja509465w","article-title":"How Does Tunneling\nContribute to\nCounterintuitive H-Abstraction Reactivity of Nonheme Fe(IV)O Oxidants\nwith Alkanes?","volume":"137","author":"Mandal","year":"2015","journal-title":"J. Am. Chem.\nSoc."},{"issue":"3","key":"2026092808082686100_cit21","doi-asserted-by":"publisher","first-page":"901","DOI":"10.1002\/anie.201208044","article-title":"A Tetracarbene\u2013Oxoiron(IV)\nComplex","volume":"52","author":"Meyer","year":"2013","journal-title":"Angew. Chem., Int. Ed."},{"issue":"43","key":"2026092808082686100_cit22","doi-asserted-by":"publisher","first-page":"14312","DOI":"10.1021\/jacs.6b07708","article-title":"Magnetic Circular Dichroism\nEvidence for an Unusual Electronic Structure of a Tetracarbene\u2013Oxoiron(IV)\nComplex","volume":"138","author":"Ye","year":"2016","journal-title":"J. Am. Chem. Soc."},{"key":"2026092808082686100_cit23a","doi-asserted-by":"publisher","first-page":"3096","DOI":"10.1021\/acs.inorgchem.5b00301","article-title":"An Exclusively Organometallic {FeNO}7 Complex with Tetracarbene Ligation and a Linear FeNO Unit","volume":"54","author":"Kupper","year":"2015","journal-title":"Inorg. Chem."},{"issue":"25","key":"2026092808082686100_cit23b","doi-asserted-by":"publisher","first-page":"7888","DOI":"10.1021\/jacs.6b00584","article-title":"Complete Series of {FeNO}8, {FeNO}7, and {FeNO}6 Complexes Stabilized by a Tetracarbene Macrocycle","volume":"138","author":"Kupper","year":"2016","journal-title":"J. Am. Chem. 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