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In the last decade, significant efforts were invested in designing bioinspired iron based catalyst systems, capable of conducting selective oxidations of organic compounds. The key role of the oxygen\u2010transferring high\u2010valent iron\u2010oxygen species in selective oxygenation is now well established; the next logical step would be gaining insight into the factors governing the oxidation chemo\u2010 and stereoselectivity, in relation to the peculiarities of their electronic structure, which would allow introducing the desired level of predictability into those catalytic transformations. In this Personal Account we analyze recent data on the reactivity of bioinspired formally oxoiron(V) catalytically active sites toward organic substrates having C=C and C(sp<jats:sup>3<\/jats:sup>)\u2212H groups. While the majority of reported oxoiron(V) active species are low\u2010spin (<jats:italic>S<\/jats:italic>=1\/2) complexes, the presence of strong electron\u2010donating groups (NR<jats:sub>1<\/jats:sub>R<jats:sub>2<\/jats:sub>) in the ligand backbone favors the high\u2010spin (<jats:italic>S<\/jats:italic>=3\/2) ground state. Remarkably, the high\u2010spin perferryl species exhibit higher chemo\u2010, regio\u2010, and stereoselectivity in the oxidations than their low\u2010spin counterparts, thus witnessing the significance of these subtle electronic effects for the selectivity of oxidations conducted by bioinspired catalysts of the Fe(PDP) family.<\/jats:p>","DOI":"10.1002\/tcr.202100334","type":"journal-article","created":{"date-parts":[[2022,2,10]],"date-time":"2022-02-10T11:56:21Z","timestamp":1644494181000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":13,"title":["Reactivity vs. Selectivity of Biomimetic Catalyst Systems of the Fe(PDP) Family through the Nature and Spin State of the Active Iron\u2010Oxygen Species"],"prefix":"10.1002","volume":"22","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-6871-223X","authenticated-orcid":false,"given":"Alexandra M.","family":"Zima","sequence":"first","affiliation":[{"name":"Boreskov Institute of Catalysis  Pr. 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