<\/p>\n\n\n Our calculations reveal the presence of an inverted ligand field\u2014an unusual electronic configuration where the lowest unoccupied molecular orbitals are predominantly ligand-based rather than metal-centered. This finding challenges conventional oxidation state descriptions and links high-valent lanthanide chemistry to transition-metal systems with similar electronic behavior.<\/p>\n\n\n\n Computational results indicate a singlet ground state with significant multiconfigurational character in [Pr5+<\/sup>(<\/em>NPt<\/sup><\/em>Bu\u2083)\u2084]+ (t<\/sup><\/em>Bu = C(CH3<\/sub>)3<\/sub>), where occupied metal-dominant orbitals (avg. %Pr = 69.9) reside at lower energies than ligand-dominant ones. Unlike the classic ligand field observed in the previously reported Pr3+<\/sup> and Pr4<\/sup>+<\/sup> imidophosphorane complexes, the antibonding orbitals in Pr5+<\/sup> exhibit greater ligand contributions (avg. %ligand = 74.5). Additionally, a notable spin density on the Pr center is counterbalanced by the four nitrogen atoms, further supporting the unique electronic structure and redox properties of early lanthanides (see Figure).<\/p>\n\n\n\n By combining experimental results with advanced computational modeling, this study underscores the vital role of theoretical chemistry in unraveling the complex electronic structures of f-block compounds and establishes a key connection in understanding the bonding of high-valent metal complexes across the periodic table.<\/p>\n","protected":false},"excerpt":{"rendered":" Congrats Chad! His article (#11!) in Nat. Chem. is highlighted in C&EN magazine!!! Check out the first Pr5+ molecular compound in a singlet ground state with significant multiconfigurational character: https:\/\/cen.acs.org\/materials\/inorganic-chemistry\/Praseodymium-powers-435\/103\/web\/2025\/04 Our calculations reveal the presence of an inverted ligand field\u2014an unusual electronic configuration where the lowest unoccupied molecular orbitals are predominantly ligand-based rather than metal-centered. […]<\/p>\n","protected":false},"author":43098,"featured_media":0,"comment_status":"open","ping_status":"open","sticky":false,"template":"","format":"standard","meta":[],"categories":[],"tags":[],"wsuwp_university_location":[],"wsuwp_university_org":[],"_links":{"self":[{"href":"https:\/\/labs.wsu.edu\/ivan-popov-lab\/wp-json\/wp\/v2\/posts\/2679"}],"collection":[{"href":"https:\/\/labs.wsu.edu\/ivan-popov-lab\/wp-json\/wp\/v2\/posts"}],"about":[{"href":"https:\/\/labs.wsu.edu\/ivan-popov-lab\/wp-json\/wp\/v2\/types\/post"}],"author":[{"embeddable":true,"href":"https:\/\/labs.wsu.edu\/ivan-popov-lab\/wp-json\/wp\/v2\/users\/43098"}],"replies":[{"embeddable":true,"href":"https:\/\/labs.wsu.edu\/ivan-popov-lab\/wp-json\/wp\/v2\/comments?post=2679"}],"version-history":[{"count":10,"href":"https:\/\/labs.wsu.edu\/ivan-popov-lab\/wp-json\/wp\/v2\/posts\/2679\/revisions"}],"predecessor-version":[{"id":2696,"href":"https:\/\/labs.wsu.edu\/ivan-popov-lab\/wp-json\/wp\/v2\/posts\/2679\/revisions\/2696"}],"wp:attachment":[{"href":"https:\/\/labs.wsu.edu\/ivan-popov-lab\/wp-json\/wp\/v2\/media?parent=2679"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/labs.wsu.edu\/ivan-popov-lab\/wp-json\/wp\/v2\/categories?post=2679"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/labs.wsu.edu\/ivan-popov-lab\/wp-json\/wp\/v2\/tags?post=2679"},{"taxonomy":"wsuwp_university_location","embeddable":true,"href":"https:\/\/labs.wsu.edu\/ivan-popov-lab\/wp-json\/wp\/v2\/wsuwp_university_location?post=2679"},{"taxonomy":"wsuwp_university_org","embeddable":true,"href":"https:\/\/labs.wsu.edu\/ivan-popov-lab\/wp-json\/wp\/v2\/wsuwp_university_org?post=2679"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}![\"\"](\"https:\/\/wpcdn.web.wsu.edu\/wp-labs\/uploads\/sites\/3458\/2025\/04\/Figure-for-highlight-792x1175.png\")
<\/figure>\n\n\n\n