{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,12]],"date-time":"2026-10-12T14:48:24Z","timestamp":1791816504428,"version":"4.3.4"},"reference-count":65,"publisher":"Wiley","license":[{"start":{"date-parts":[[2026,10,9]],"date-time":"2026-10-09T00:00:00Z","timestamp":1791504000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"},{"start":{"date-parts":[[2026,10,9]],"date-time":"2026-10-09T00:00:00Z","timestamp":1791504000000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"funder":[{"DOI":"10.13039\/501100000266","name":"Engineering and Physical Sciences Research Council","doi-asserted-by":"publisher","award":["EP\/Z535278\/1"],"award-info":[{"award-number":["EP\/Z535278\/1"]}],"id":[{"id":"10.13039\/501100000266","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100000266","name":"Engineering and Physical Sciences Research Council","doi-asserted-by":"publisher","award":["EP\/Y019954\/1"],"award-info":[{"award-number":["EP\/Y019954\/1"]}],"id":[{"id":"10.13039\/501100000266","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Angew Chem Int Ed"],"abstract":"<jats:title>ABSTRACT<\/jats:title>\n                  <jats:p>\n                    Iron bisphosphine complexes represent an important class of sustainable catalysts for a variety of important chemical transformations due to the high abundance, low toxicity, and redox\u2010rich chemistry inherent to iron\u2010based systems. In particular, transient, low\u2010coordinate Fe(I) species are postulated to play a pivotal role in multiple catalytic transformations as the principal species for C\u2500X bond activation (X\u00a0=\u00a0Cl, Br, I). However, insight into the electronic structure, bonding, and reactivity of Fe(I)\u2010bisphosphine complexes remains poorly developed. In the present study, we report the development of four\u2010coordinate (4C), high\u2010spin (\n                    <jats:italic>S<\/jats:italic>\n                    \u00a0=\u00a03\/2) Fe(I)\u2010bisphosphine\u2010ates. Several novel Fe(I) complexes were structurally characterized, and their electronic structure and bonding were evaluated using a combined spectroscopic, synthetic, and computational approach. Additionally, this study highlights the potential role of charged species in synthetically relevant contexts via in situ formation of (4C) Fe(I)\u2010bisphosphine\u2010ates in the presence of ubiquitous additives (e.g. MgBr\n                    <jats:sub>2<\/jats:sub>\n                    ). Lastly, we demonstrate the utility of these Fe(I)\u2010bisphosphine\u2010ates toward rapid C\u2500X homolytic cleavage of common alkyl\u2010 and aryl\u2010halide electrophiles, as well as the ability to serve as synthons for further development of new high\u2010spin Fe(I)\u2010bisphosphine\u2010ate complexes through transmetalation.\n                  <\/jats:p>","DOI":"10.1002\/anie.7300550","type":"journal-article","created":{"date-parts":[[2026,10,10]],"date-time":"2026-10-10T02:57:18Z","timestamp":1791601038000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["<i>S<\/i>\n                    = 3\/2 Iron(I)\u2010Bisphosphine\u2010Ate Complexes: Synthesis, Characterization, and Reactivity for Electrophile Activation"],"prefix":"10.1002","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-6412-7818","authenticated-orcid":false,"given":"Egor","family":"Kokin","sequence":"first","affiliation":[{"name":"Inorganic Chemistry Laboratory Department of Chemistry University of Oxford  Oxford UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0000-3836-8458","authenticated-orcid":false,"given":"Shih\u2010Chieh","family":"Kao","sequence":"additional","affiliation":[{"name":"Inorganic Chemistry Laboratory Department of Chemistry University of Oxford  Oxford UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4445-9780","authenticated-orcid":false,"given":"Matthew J.","family":"Kania","sequence":"additional","affiliation":[{"name":"Inorganic Chemistry Laboratory Department of Chemistry University of Oxford  Oxford UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2300-3867","authenticated-orcid":false,"given":"Michael L.","family":"Neidig","sequence":"additional","affiliation":[{"name":"Inorganic Chemistry Laboratory Department of Chemistry University of Oxford  Oxford UK"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2026,10,9]]},"reference":[{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja01011a012"},{"key":"e_1_2_8_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00435a068"},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00072a016"},{"key":"e_1_2_8_5_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41929\u2010023\u201001105\u20100"},{"key":"e_1_2_8_6_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.4c12329"},{"key":"e_1_2_8_7_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.5c12754"},{"key":"e_1_2_8_8_1","doi-asserted-by":"publisher","DOI":"10.1021\/om00135a039"},{"key":"e_1_2_8_9_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.6c01157"},{"key":"e_1_2_8_10_1","doi-asserted-by":"publisher","DOI":"10.1246\/cl.2011.1030"},{"key":"e_1_2_8_11_1","doi-asserted-by":"publisher","DOI":"10.1246\/cl.2013.183"},{"key":"e_1_2_8_12_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.abj6005"},{"key":"e_1_2_8_13_1","doi-asserted-by":"publisher","DOI":"10.1039\/B818961G"},{"key":"e_1_2_8_14_1","doi-asserted-by":"publisher","DOI":"10.1039\/b820879d"},{"key":"e_1_2_8_15_1","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.200600383"},{"key":"e_1_2_8_16_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201202797"},{"key":"e_1_2_8_17_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201207868"},{"key":"e_1_2_8_18_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201402174"},{"key":"e_1_2_8_19_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja103973a"},{"key":"e_1_2_8_20_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.5b02277"},{"key":"e_1_2_8_21_1","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.201301089"},{"key":"e_1_2_8_22_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202413566"},{"key":"e_1_2_8_23_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.3c03059"},{"key":"e_1_2_8_24_1","doi-asserted-by":"publisher","DOI":"10.1039\/D3SC04549H"},{"key":"e_1_2_8_25_1","doi-asserted-by":"publisher","DOI":"10.1039\/D1CC04619E"},{"key":"e_1_2_8_26_1","doi-asserted-by":"publisher","DOI":"10.1039\/D0SC02127J"},{"key":"e_1_2_8_27_1","doi-asserted-by":"publisher","DOI":"10.1039\/D0SC00467G"},{"key":"e_1_2_8_28_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00015a050"},{"key":"e_1_2_8_29_1","doi-asserted-by":"publisher","DOI":"10.1039\/dt9930003041"},{"key":"e_1_2_8_30_1","doi-asserted-by":"publisher","DOI":"10.1039\/dt9960003539"},{"key":"e_1_2_8_31_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic00109a046"},{"key":"e_1_2_8_32_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja053030g"},{"key":"e_1_2_8_33_1","doi-asserted-by":"publisher","DOI":"10.1039\/c39930000787"},{"key":"e_1_2_8_34_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.5b00211"},{"key":"e_1_2_8_35_1","doi-asserted-by":"publisher","DOI":"10.1039\/C6DT00884D"},{"key":"e_1_2_8_36_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja503596m"},{"key":"e_1_2_8_37_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.5b06648"},{"key":"e_1_2_8_38_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.7b02363"},{"key":"e_1_2_8_39_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.5b02263"},{"key":"e_1_2_8_40_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.7b06377"},{"key":"e_1_2_8_41_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.7b05917"},{"key":"e_1_2_8_42_1","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201109204"},{"key":"e_1_2_8_43_1","doi-asserted-by":"publisher","DOI":"10.1039\/D0SC03447A"},{"key":"e_1_2_8_44_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41586\u2010020\u20102565\u20105"},{"key":"e_1_2_8_45_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja303250t"},{"key":"e_1_2_8_46_1","doi-asserted-by":"publisher","DOI":"10.1021\/om500518r"},{"key":"e_1_2_8_47_1","doi-asserted-by":"publisher","DOI":"10.1021\/om500847j"},{"key":"e_1_2_8_48_1","doi-asserted-by":"publisher","DOI":"10.1039\/C8SC01841C"},{"key":"e_1_2_8_49_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201909050"},{"key":"e_1_2_8_50_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.6c01660"},{"key":"e_1_2_8_51_1","doi-asserted-by":"publisher","DOI":"10.1039\/C8CC07466F"},{"key":"e_1_2_8_52_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.7b04552"},{"key":"e_1_2_8_53_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00060a022"},{"key":"e_1_2_8_54_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic3024953"},{"key":"e_1_2_8_55_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201603574"},{"key":"e_1_2_8_56_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202202030"},{"key":"e_1_2_8_57_1","unstructured":"Deposition 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These data are provided free of charge by the joint Cambridge Crystallographic Data Centre and Fachinformationszentrum Karlsruhe."},{"key":"e_1_2_8_58_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00068a035"},{"key":"e_1_2_8_59_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic801704n"},{"key":"e_1_2_8_60_1","unstructured":"BS1 = 6\u201031G(d) (C H)\/Def2\u2010TZVP(Fe P Br). 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