{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,13]],"date-time":"2025-10-13T20:40:46Z","timestamp":1760388046417,"version":"build-2065373602"},"reference-count":28,"publisher":"Wiley","issue":"22","license":[{"start":{"date-parts":[[2012,7,4]],"date-time":"2012-07-04T00:00:00Z","timestamp":1341360000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Eur J Inorg Chem"],"published-print":{"date-parts":[[2012,8]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The electronic structures of LnNH<jats:sup>+<\/jats:sup> species are studied by DFT (B3LYP) quantum calculations for the Ln = La, Eu and Gd 4f\u2010block elements (lanthanides). Ln\u2261N triple bonds of essentially d character are formed for La and Gd, which explains why La<jats:sup>+<\/jats:sup> and Gd<jats:sup>+<\/jats:sup> behave like ions of d\u2010block transition metals, as experimentally evidenced by mass spectrometry, and why the Ln<jats:sup>+<\/jats:sup> reactivity is correlated with its electron\u2010promotion energy: the present theoretical study is a support to such a correlation and qualitative knowledge. The Ln<jats:sup>+<\/jats:sup> + NH<jats:sub>3<\/jats:sub> \u2192 LnNH<jats:sub>3<\/jats:sub><jats:sup>+<\/jats:sup> \u2192 transition state \u2192 HLn=NH<jats:sub>2<\/jats:sub><jats:sup>+<\/jats:sup> \u2192 transition state \u2192 Ln\u2261NH<jats:sup>+<\/jats:sup> + H<jats:sub>2<\/jats:sub> reaction pathway is calculated. The formation of H\u2013Ln=NH<jats:sub>2<\/jats:sub><jats:sup>+<\/jats:sup> corresponds to the formation of new covalent bonds associated with more electron pairing and corresponding lowering of the spin multiplicity\u2013spin crossing reaction. It is in this step that low electron\u2010promotion energy is required to promote a 4f electron into a 5d orbital as is typical for La<jats:sup>+<\/jats:sup> and Gd<jats:sup>+<\/jats:sup>. A similar geometry, bonding and electronic configuration are calculated for NpNH<jats:sup>+<\/jats:sup> \u2013 an actinide complex observed by mass spectrometry \u2013 with higher participation of 5f orbitals (20\u2009% and 25\u2009% for the \u03c3 and \u03c0 bonds, respectively) as compared to the 4f orbitals (3\u2009% and 8\u2009%) of GdNH<jats:sup>+<\/jats:sup>: Gd<jats:sup>+<\/jats:sup> and Np<jats:sup>+<\/jats:sup> are the only lanthanide and actinide monocations with one s\u2010 and one d\u2010valence electrons in their ground states.<\/jats:p>","DOI":"10.1002\/ejic.201200455","type":"journal-article","created":{"date-parts":[[2012,7,4]],"date-time":"2012-07-04T20:40:47Z","timestamp":1341434447000},"page":"3551-3555","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":6,"title":["How Can f\u2010Block Monocations Behave as Monocations of d\u2010Block Transition Metals?"],"prefix":"10.1002","volume":"2012","author":[{"given":"Alexandre","family":"Quemet","sequence":"first","affiliation":[]},{"given":"Rene","family":"Brennetot","sequence":"additional","affiliation":[]},{"given":"Jean\u2010Yves","family":"Salpin","sequence":"additional","affiliation":[]},{"given":"Alvaro","family":"Cimas","sequence":"additional","affiliation":[]},{"given":"Colin","family":"Marsden","sequence":"additional","affiliation":[]},{"given":"Jeanine","family":"Tortajada","sequence":"additional","affiliation":[]},{"given":"Pierre","family":"Vitorge","sequence":"additional","affiliation":[]}],"member":"311","published-online":{"date-parts":[[2012,7,4]]},"reference":[{"key":"e_1_2_4_1_2","unstructured":"\u00a0"},{"key":"e_1_2_4_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp9079487"},{"key":"e_1_2_4_3_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ijms.2005.11.025"},{"key":"e_1_2_4_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic061000o"},{"key":"e_1_2_4_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp011627m"},{"key":"e_1_2_4_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp0637431"},{"key":"e_1_2_4_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00209a002"},{"key":"e_1_2_4_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/om00002a053"},{"key":"e_1_2_4_9_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp960882h"},{"key":"e_1_2_4_10_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ijms.2004.01.018"},{"key":"e_1_2_4_11_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp900671c"},{"key":"e_1_2_4_12_2","unstructured":"\u00a0"},{"key":"e_1_2_4_13_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00338a019"},{"key":"e_1_2_4_14_2","doi-asserted-by":"publisher","DOI":"10.1021\/om00145a018"},{"key":"e_1_2_4_15_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201102494"},{"key":"e_1_2_4_16_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-328X(01)01407-3"},{"key":"e_1_2_4_17_2","unstructured":"\u00a0"},{"key":"e_1_2_4_18_2","doi-asserted-by":"publisher","DOI":"10.1107\/S0567739476001551"},{"key":"e_1_2_4_19_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic200260r"},{"key":"e_1_2_4_20_2","unstructured":"A. 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