{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,18]],"date-time":"2026-09-18T13:06:01Z","timestamp":1789736761293,"version":"4.0.1"},"reference-count":19,"publisher":"Wiley","issue":"35","license":[{"start":{"date-parts":[[2026,6,3]],"date-time":"2026-06-03T00:00:00Z","timestamp":1780444800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"},{"start":{"date-parts":[[2026,6,3]],"date-time":"2026-06-03T00:00:00Z","timestamp":1780444800000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"funder":[{"DOI":"10.13039\/501100008530","name":"European Regional Development Fund","doi-asserted-by":"publisher","id":[{"id":"10.13039\/501100008530","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2026,9,19]]},"abstract":"<jats:title>ABSTRACT<\/jats:title>\n                  <jats:p>\n                    Reported here are DFT calculations on porphyrin, corrin, and corphin complexes with formally metal (I) states of cobalt, rhodium, iron, manganese, or nickel, complemented by QM\/MM calculations on enzyme models, and exploring the available spin states, with the goal to understand factors controlling the availably of super\u2010reduced metal(I) states on such biologically\u2010relevant systems. In the porphyrin systems, the preferred spin states offer no clear case of metal(I) electronic description\u2014but rather metal(II) coupled with porphyrin anion radicals; this is in line with the fact that porphyrin is not used in biology for mechanisms\/reactions entailing super\u2010reduced metals. The corrin, somewhat less conjugated than the porphyrin, affords a clear\u2010cut ground\u2010state S = 0 Co(I) complex, with essentially no delocalization of the extra electron onto the macrocycle. None of the neighbors of cobalt in the third period afford clear super\u2010reduced ground states with corrin\u2014in line with cobalamin's choice of metal in biology, cobalt. The least conjugated system, the corphin (as seen in F\n                    <jats:sub>430<\/jats:sub>\n                    ), now affords a metal(I) state even in the case of Ni. Moreover, in fact, only Ni affords a ground state with clear super\u2010reduced character\u2014in line with F\n                    <jats:sub>430<\/jats:sub>\n                    \u2018s choice of metal in vivo.\n                  <\/jats:p>","DOI":"10.1002\/chem.71214","type":"journal-article","created":{"date-parts":[[2026,6,4]],"date-time":"2026-06-04T04:09:21Z","timestamp":1780546161000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Rationales for the Choice of Metals for Super\u2010Reduced Biological Metal Centers: Cobalt in Cobalamin Versus Nickel in F\n                    <sub>430<\/sub>"],"prefix":"10.1002","volume":"32","author":[{"given":"Radu\u2010Ioan","family":"Onija","sequence":"first","affiliation":[{"name":"Faculty of Chemistry and Chemical Engineering and INSPIRE Platform Infobionano4health &amp; Biomedical Imaging Babe\u0219\u2010Bolyai University  Cluj\u2010Napoca Romania"},{"name":"National Institute for Research and Development of Isotopic and Molecular Technologies  Cluj\u2010Napoca Romania"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sergiu\u2010Raul","family":"Cosma","sequence":"additional","affiliation":[{"name":"Faculty of Chemistry and Chemical Engineering and INSPIRE Platform Infobionano4health &amp; Biomedical Imaging Babe\u0219\u2010Bolyai University  Cluj\u2010Napoca Romania"},{"name":"\u201cRaluca Ripan\u201d Institute for Research in Chemistry Babe\u0219\u2010Bolyai University  Cluj\u2010Napoca Romania"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Adrian M. V.","family":"Br\u00e2nzanic","sequence":"additional","affiliation":[{"name":"Faculty of Chemistry and Chemical Engineering and INSPIRE Platform Infobionano4health &amp; Biomedical Imaging Babe\u0219\u2010Bolyai University  Cluj\u2010Napoca Romania"},{"name":"\u201cRaluca Ripan\u201d Institute for Research in Chemistry Babe\u0219\u2010Bolyai University  Cluj\u2010Napoca Romania"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3038-7747","authenticated-orcid":false,"given":"Radu","family":"Silaghi\u2010Dumitrescu","sequence":"additional","affiliation":[{"name":"Faculty of Chemistry and Chemical Engineering and INSPIRE Platform Infobionano4health &amp; Biomedical Imaging Babe\u0219\u2010Bolyai University  Cluj\u2010Napoca Romania"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2026,6,3]]},"reference":[{"key":"e_1_2_7_2_1","doi-asserted-by":"publisher","DOI":"10.1093\/oso\/9780198553809.001.0001"},{"key":"e_1_2_7_3_1","doi-asserted-by":"publisher","DOI":"10.1074\/jbc.REV120.006194"},{"key":"e_1_2_7_4_1","doi-asserted-by":"publisher","DOI":"10.1039\/d1cc02945b"},{"key":"e_1_2_7_5_1","doi-asserted-by":"publisher","DOI":"10.1016\/0014\u20105793(79)80113\u20101"},{"key":"e_1_2_7_6_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.ultsonch.2010.08.010"},{"key":"e_1_2_7_7_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201904713"},{"key":"e_1_2_7_8_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201908428"},{"key":"e_1_2_7_9_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201301146"},{"key":"e_1_2_7_10_1","doi-asserted-by":"publisher","DOI":"10.1002\/ANIE.202008407"},{"key":"e_1_2_7_11_1","doi-asserted-by":"publisher","DOI":"10.1002\/ANIE.201603738"},{"key":"e_1_2_7_12_1","doi-asserted-by":"publisher","DOI":"10.1142\/S1088424605000691"},{"key":"e_1_2_7_13_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2008.04.015"},{"key":"e_1_2_7_14_1","doi-asserted-by":"publisher","DOI":"10.1021\/JACS.3C00469\/ASSET\/IMAGES\/LARGE\/JA3C00469_0011.JPEG"},{"key":"e_1_2_7_15_1","doi-asserted-by":"publisher","DOI":"10.1039\/B919517C"},{"key":"e_1_2_7_16_1","doi-asserted-by":"publisher","DOI":"10.1007\/s00775\u2010010\u20100659\u20105"},{"key":"e_1_2_7_17_1","doi-asserted-by":"publisher","DOI":"10.1021\/JP963142H"},{"key":"e_1_2_7_18_1","doi-asserted-by":"publisher","DOI":"10.1042\/BST0330806"},{"key":"e_1_2_7_19_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201502072"},{"key":"e_1_2_7_20_1","doi-asserted-by":"publisher","DOI":"10.1042\/BST0330806"}],"container-title":["Chemistry \u2013 A European Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.71214","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/chem.71214","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.71214","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,9,18]],"date-time":"2026-09-18T12:27:29Z","timestamp":1789734449000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/chem.71214"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,6,3]]},"references-count":19,"journal-issue":{"issue":"35","published-print":{"date-parts":[[2026,9,19]]}},"alternative-id":["10.1002\/chem.71214"],"URL":"https:\/\/doi.org\/10.1002\/chem.71214","archive":["Portico"],"relation":{},"ISSN":["0947-6539","1521-3765"],"issn-type":[{"value":"0947-6539","type":"print"},{"value":"1521-3765","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,6,3]]},"assertion":[{"value":"2026-03-10","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2026-05-18","order":2,"name":"accepted","label":"Accepted","group":{"name":"publication_history","label":"Publication History"}},{"value":"2026-06-03","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e71214"}}