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The study considers the usual heme porphyrin (complex I) as the base compound, porphyrazine (complex II), which is obtained by replacing carbon with nitrogen at the meso position, and phthalocyanine (complex III), which is obtained through the peripheral benzoannulation of porphyrazine. The main focus here is to explore the impact of bridging groups and peripheral functionalization in heme systems on reactivity. Chloride is used as the axial ligand for all complexes and dihydroanthracene (DHA) is used as the substrate. Factors such as distortion energy and different electron acceptor orbitals significantly affect the overall reactivity. The effect of substitution on quantum mechanical tunneling, using H\/D kinetic isotope effect studies, is also included. The results reveal a fascinating reactivity order: meso nitrogen substitution enhances reactivity, while additional benzo\u2010annulation hinders reactivity, leading to the order complex II &gt;complex I &gt;complex III. In comparison to the usual model compound I, which is Fe(IV)O\u2010porphyrin \u03c0 cation radical with an \u2212SH axial ligand, complex II was found to be more reactive. The electron affinity of the Fe(IV)O complexes and the dissociation energy of the forming Fe(IV)O\u2212H bond aligns with observed reactivity trend. These findings support the use of accessible iron frameworks derived from porphyrin in C\u2212H activation processes.<\/jats:p>","DOI":"10.1002\/cphc.202400765","type":"journal-article","created":{"date-parts":[[2024,11,3]],"date-time":"2024-11-03T22:20:22Z","timestamp":1730672422000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Insights into C\u2212H Activation Reactivity of Fe (IV)O Porphyrinoid Complexes: A Computational Investigation"],"prefix":"10.1002","volume":"26","author":[{"given":"Lovleen","family":"Kaur","sequence":"first","affiliation":[{"name":"Department of Chemistry and Biochemistry Thapar Institute of Engineering and Technology  Patiala, Punjab 147004 India"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9452-6729","authenticated-orcid":false,"given":"Debasish","family":"Mandal","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Biochemistry Thapar Institute of Engineering and Technology  Patiala, Punjab 147004 India"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2024,11,20]]},"reference":[{"key":"e_1_2_8_1_1","doi-asserted-by":"publisher","DOI":"10.1002\/1099-0682(200012)2000:12<2455::AID-EJIC2455>3.0.CO;2-4"},{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2012.08.002"},{"key":"e_1_2_8_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr020628n"},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar700027f"},{"key":"e_1_2_8_5_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar400258p"},{"key":"e_1_2_8_6_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41570-020-0197-9"},{"key":"e_1_2_8_7_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar700066p"},{"key":"e_1_2_8_8_1","doi-asserted-by":"publisher","DOI":"10.1111\/j.1742-4658.2011.08412.x"},{"key":"e_1_2_8_9_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr00027a011"},{"key":"e_1_2_8_10_1","doi-asserted-by":"publisher","DOI":"10.1136\/jmg.17.1.1"},{"key":"e_1_2_8_11_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.472082"},{"key":"e_1_2_8_12_1","first-page":"201","volume-title":"Porphyr. 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