{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,9]],"date-time":"2026-10-09T11:10:56Z","timestamp":1791544256783,"version":"4.3.4"},"reference-count":80,"publisher":"Wiley","license":[{"start":{"date-parts":[[2024,9,17]],"date-time":"2024-09-17T00:00:00Z","timestamp":1726531200000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by-nc\/4.0\/"}],"funder":[{"DOI":"10.13039\/100000001","name":"National Science Foundation","doi-asserted-by":"publisher","award":["1943452"],"award-info":[{"award-number":["1943452"]}],"id":[{"id":"10.13039\/100000001","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100000001","name":"National Science Foundation","doi-asserted-by":"publisher","award":["CHE2246913"],"award-info":[{"award-number":["CHE2246913"]}],"id":[{"id":"10.13039\/100000001","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100000015","name":"U.S. Department of Energy","doi-asserted-by":"publisher","award":["DESC0023022"],"award-info":[{"award-number":["DESC0023022"]}],"id":[{"id":"10.13039\/100000015","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100000015","name":"U.S. Department of Energy","doi-asserted-by":"publisher","award":["DE-AC02-76SF00515"],"award-info":[{"award-number":["DE-AC02-76SF00515"]}],"id":[{"id":"10.13039\/100000015","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100000009","name":"Foundation for the National Institutes of Health","doi-asserted-by":"publisher","award":["P30GM133894"],"award-info":[{"award-number":["P30GM133894"]}],"id":[{"id":"10.13039\/100000009","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><jats:p>The imidophosphorane ligand, [NP<jats:sup><jats:italic>t<\/jats:italic><\/jats:sup>Bu<jats:sub>3<\/jats:sub>]<jats:sup>\u2212<\/jats:sup> (<jats:sup><jats:italic>t<\/jats:italic><\/jats:sup>Bu=<jats:italic>tert<\/jats:italic>\u2010butyl), enables isolation of a pseudo\u2010tetrahedral, tetravalent praseodymium complex, [Pr<jats:sup>4+<\/jats:sup>(NP<jats:sup><jats:italic>t<\/jats:italic><\/jats:sup>Bu<jats:sub>3<\/jats:sub>)<jats:sub>4<\/jats:sub>] (<jats:bold>1\u2010Pr<\/jats:bold>), which is characterized by a suite of physical characterization methods including single\u2010crystal X\u2010ray diffraction, electron paramagnetic resonance, and L<jats:sub>3<\/jats:sub>\u2010edge X\u2010ray near\u2010edge spectroscopies. Variable\u2010temperature direct\u2010current magnetic susceptibility data, supported by multiconfigurational quantum chemical calculations, demonstrate that the electronic structure diverges from the isoelectronic Ce<jats:sup>3+<\/jats:sup> analogue, driven by increased crystal field. The four\u2010coordinate environment around Pr<jats:sup>4+<\/jats:sup> in <jats:bold>1\u2010Pr<\/jats:bold>, which is unparalleled in reported extended solid systems, provides a unique opportunity to study the interplay between crystal field splitting and spin\u2010orbit coupling in a molecular tetravalent lanthanide within a pseudo\u2010tetrahedral coordination geometry.<\/jats:p>","DOI":"10.1002\/anie.202409789","type":"journal-article","created":{"date-parts":[[2024,7,16]],"date-time":"2024-07-16T16:15:02Z","timestamp":1721146502000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":20,"title":["A Four\u2010Coordinate Pr<sup>4+<\/sup> Imidophosphorane Complex"],"prefix":"10.1002","author":[{"given":"Andrew C.","family":"Boggiano","sequence":"first","affiliation":[{"name":"School of Chemistry &amp; Biochemistry Georgia Institute of Technology  Atlanta GA 30332-0400 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sabyasachi Roy","family":"Chowdhury","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of South Dakota  Vermillion SD 57069 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Michael D.","family":"Roy","sequence":"additional","affiliation":[{"name":"School of Chemistry &amp; Biochemistry Georgia Institute of Technology  Atlanta GA 30332-0400 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Maximilian G.","family":"Bernbeck","sequence":"additional","affiliation":[{"name":"School of Chemistry &amp; Biochemistry Georgia Institute of Technology  Atlanta GA 30332-0400 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Samuel M.","family":"Greer","sequence":"additional","affiliation":[{"name":"Chemistry Division Los Alamos National Laboratory  Los Alamos NM 87545 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Bess","family":"Vlaisavljevich","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of South Dakota  Vermillion SD 57069 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0895-0655","authenticated-orcid":false,"given":"Henry S.","family":"La Pierre","sequence":"additional","affiliation":[{"name":"School of Chemistry &amp; Biochemistry Georgia Institute of Technology  Atlanta GA 30332-0400 USA"},{"name":"Nuclear and Radiological Engineering and Medical Physics Program School of Mechanical Engineering Georgia Institute of Technology  Atlanta GA 30332-0400 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2024,9,17]]},"reference":[{"key":"e_1_2_3_1_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.9b06622"},{"key":"e_1_2_3_2_1","doi-asserted-by":"publisher","DOI":"10.1039\/D2DT00758D"},{"key":"e_1_2_3_3_1","unstructured":"\u00a0"},{"key":"e_1_2_3_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.9b05337"},{"key":"e_1_2_3_5_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201914733"},{"key":"e_1_2_3_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/prechem.3c00065"},{"key":"e_1_2_3_7_2","doi-asserted-by":"publisher","DOI":"10.1039\/D4SC00051J"},{"key":"e_1_2_3_8_1","unstructured":"\u00a0"},{"key":"e_1_2_3_9_2","doi-asserted-by":"publisher","DOI":"10.1039\/D1SC05517H"},{"key":"e_1_2_3_10_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.0c01204"},{"key":"e_1_2_3_11_2","doi-asserted-by":"publisher","DOI":"10.1039\/D4DT00052H"},{"key":"e_1_2_3_12_1","unstructured":"\u00a0"},{"key":"e_1_2_3_13_2","doi-asserted-by":"publisher","DOI":"10.1039\/D0DT01400A"},{"key":"e_1_2_3_14_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2013.08.034"},{"key":"e_1_2_3_15_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.3c02820"},{"key":"e_1_2_3_16_1","doi-asserted-by":"crossref","first-page":"3134","DOI":"10.1038\/s41467-023-38431-7","volume":"14","author":"Ramanathan A.","year":"2023","journal-title":"Nat. Commun."},{"key":"e_1_2_3_17_1","unstructured":"The electrochemical characterization of the complexes reported herein will be described in a separate manuscript."},{"key":"e_1_2_3_18_1","unstructured":"The CCDC numbers 2296902 (1-Ce) 2296905 (1-Pr) 2296901 (2-CeCs) 2296904 (2-PrCs) 2296903 (KNPtBu3\u22c5tol0.25) contain the supplementary crystallographic data. These data are provided free of charge by the joint Cambridge Crystallographic Data Centre and Fachinformationszentrum Karlsruhe Access Structures service."},{"key":"e_1_2_3_19_1","doi-asserted-by":"publisher","DOI":"10.1107\/S0567739476001551"},{"key":"e_1_2_3_20_1","doi-asserted-by":"publisher","DOI":"10.1039\/B617136B"},{"key":"e_1_2_3_21_1","doi-asserted-by":"publisher","DOI":"10.1021\/j100377a011"},{"key":"e_1_2_3_22_1","unstructured":"\u00a0"},{"key":"e_1_2_3_23_2","doi-asserted-by":"publisher","DOI":"10.1039\/D3SC04262F"},{"key":"e_1_2_3_24_2","doi-asserted-by":"publisher","DOI":"10.1039\/D0SC01414A"},{"key":"e_1_2_3_25_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.9b00368"},{"key":"e_1_2_3_26_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202306580"},{"key":"e_1_2_3_27_1","unstructured":"\u00a0"},{"key":"e_1_2_3_28_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0009-2614(02)00498-0"},{"key":"e_1_2_3_29_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.3596699"},{"key":"e_1_2_3_30_1","unstructured":"\u00a0"},{"key":"e_1_2_3_31_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.7b10361"},{"key":"e_1_2_3_32_2","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevB.36.1750"},{"key":"e_1_2_3_33_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja510067v"},{"key":"e_1_2_3_34_1","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevB.35.806"},{"key":"e_1_2_3_35_1","doi-asserted-by":"publisher","DOI":"10.1039\/D3SC03304J"},{"key":"e_1_2_3_36_1","unstructured":"\u00a0"},{"key":"e_1_2_3_37_2","doi-asserted-by":"publisher","DOI":"10.1006\/jssc.1996.7193"},{"key":"e_1_2_3_38_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0925-8388(96)02557-1"},{"key":"e_1_2_3_39_2","doi-asserted-by":"publisher","DOI":"10.1006\/jssc.1996.0131"},{"key":"e_1_2_3_40_2","doi-asserted-by":"publisher","DOI":"10.1006\/jssc.1998.8106"},{"key":"e_1_2_3_41_2","doi-asserted-by":"publisher","DOI":"10.1006\/jssc.1994.1263"},{"key":"e_1_2_3_42_1","unstructured":"\u00a0"},{"key":"e_1_2_3_43_2","doi-asserted-by":"publisher","DOI":"10.1088\/0370-1328\/73\/6\/413"},{"key":"e_1_2_3_44_2","doi-asserted-by":"publisher","DOI":"10.1088\/0370-1328\/73\/6\/412"},{"key":"e_1_2_3_45_1","unstructured":"R.\u2005S. Drago Physical Methods for Chemists Surfside Scientific Publishers 1992."},{"key":"e_1_2_3_46_1","unstructured":"\u00a0"},{"key":"e_1_2_3_47_2","doi-asserted-by":"publisher","DOI":"10.1016\/0022-4596(88)90205-8"},{"key":"e_1_2_3_48_2","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevB.103.L121109"},{"key":"e_1_2_3_49_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.1724864"},{"key":"e_1_2_3_50_2","doi-asserted-by":"crossref","first-page":"3177","DOI":"10.1063\/1.1725693","volume":"41","author":"MacChesney J. B.","year":"1964","journal-title":"J. Chem. Phys."},{"key":"e_1_2_3_51_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.1c01062"},{"key":"e_1_2_3_52_1","unstructured":"\u00a0"},{"key":"e_1_2_3_53_2","doi-asserted-by":"publisher","DOI":"10.1038\/ncomms14137"},{"key":"e_1_2_3_54_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja403815h"},{"key":"e_1_2_3_55_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.chempr.2021.05.001"},{"key":"e_1_2_3_56_2","first-page":"181","volume":"255","author":"Eisenstein J. C.","year":"1997","journal-title":"Proc. R. Soc. London"},{"key":"e_1_2_3_57_2","first-page":"2225","volume-title":"The Chemistry of the Actinide and Transactinide Elements","author":"Edelstein N. M.","year":"2011"},{"key":"e_1_2_3_58_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.organomet.5b00212"},{"key":"e_1_2_3_59_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.4c01964"},{"key":"e_1_2_3_60_1","doi-asserted-by":"publisher","DOI":"10.1107\/S0909049505012719"},{"key":"e_1_2_3_61_1","unstructured":"M. Newville R. Otten A. Nelson T. Stensitzki A. Ingargiola D. Allan A. Fox F. Carter Michal R. Osborn D. Pustakhod Ineuhaus S. Weigand A. Aristov Glenn C. Deil mgunyho Mark A.\u2005L.\u2005R. Hansen G. Pasquevich L. Foks N. Zobrist O. Frost Steurmer azelcer A. Polloreno A. Persaud J. Hedegaard Nielsen M. Pompili P. Eendebak Vol. 1.2.2 Zenodo 2023."},{"key":"e_1_2_3_62_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.8b00928"},{"key":"e_1_2_3_63_1","unstructured":"\u00a0"},{"key":"e_1_2_3_64_2","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevLett.95.267202"},{"key":"e_1_2_3_65_2","doi-asserted-by":"publisher","DOI":"10.1021\/om7012327"},{"key":"e_1_2_3_66_1","doi-asserted-by":"publisher","DOI":"10.1021\/ed085p532"},{"key":"e_1_2_3_67_1","unstructured":"O. Kahn Molecular Magnetism Dover Publications 2021."},{"key":"e_1_2_3_68_1","unstructured":"V8.40B ed. Bruker Madison WI USA."},{"key":"e_1_2_3_69_1","doi-asserted-by":"publisher","DOI":"10.1107\/S1600576714022985"},{"key":"e_1_2_3_70_1","doi-asserted-by":"publisher","DOI":"10.1107\/S2053229614024218"},{"key":"e_1_2_3_71_1","doi-asserted-by":"publisher","DOI":"10.1107\/S0021889808042726"},{"key":"e_1_2_3_72_1","doi-asserted-by":"publisher","DOI":"10.1016\/0301-0104(80)80045-0"},{"key":"e_1_2_3_73_1","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevA.33.3742"},{"key":"e_1_2_3_74_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp803213j"},{"key":"e_1_2_3_75_1","doi-asserted-by":"publisher","DOI":"10.1021\/ct700263h"},{"key":"e_1_2_3_76_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.4739763"},{"key":"e_1_2_3_77_1","doi-asserted-by":"publisher","DOI":"10.1021\/ct500483t"},{"key":"e_1_2_3_78_1","doi-asserted-by":"publisher","DOI":"10.1039\/D0FD00037J"},{"key":"e_1_2_3_79_1","doi-asserted-by":"publisher","DOI":"10.1021\/ct100478d"},{"key":"e_1_2_3_80_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jctc.3c00182"}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.202409789","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2024,9,17]],"date-time":"2024-09-17T19:57:14Z","timestamp":1726603034000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.202409789"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2024,9,17]]},"references-count":80,"alternative-id":["10.1002\/anie.202409789"],"URL":"https:\/\/doi.org\/10.1002\/anie.202409789","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2024,9,17]]},"assertion":[{"value":"2024-05-23","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2024-09-17","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e202409789"}}