Isolation and Characterization of a Pentakis(imido)uranate(VI) Tetraanion

Isolation and Characterization of a Pentakis(imido)uranate(VI) Tetraanion | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article Isolation and Characterization of a Pentakis(imido)uranate(VI) Tetraanion Suzanne Bart, Kelly Gullett, Clara Silva, Arturo Sauza-de la Vega, and 13 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-7967522/v1 This work is licensed under a CC BY 4.0 License Status: Under Review Version 1 posted You are reading this latest preprint version Abstract Metal-imido species, those featuring metal-nitrogen multiple bonds M=NR, are common in organometallic chemistry as intermediates in homogeneous catalytic transformations and for supporting highly oxidized non-oxo metal cations. 1 Those featuring multiple imido groups, especially three 2-6 or four, 7,8 are rare reflecting their difficult synthesis and ability of a single metal ion to support the increased π loading. Here, we show the synthesis, isolation, and characterization of the first pentakis(imido) derivative for any metal, the pentakis(imido)uranate(VI) tetra(anion), (K-Et 2 O) 4 [U(NDIPP) 5 ]. This species features five terminal uranium-nitrogen multiple bonds with four intercalated potassium cations forcing a geometry that is between trigonal bipyramidal and square pyramidal (t = 0.51). Density functional theory calculations and chemical bonding analysis estimate the U-N bond orders range from 1.5 to 2.0. These values are significantly lower than for previously reported uranium(VI) tris(imido) species 9,10 and tetrakis(imido)uranate(VI) dianions, 7 supporting the hypothesis that strong U-N multiple bonds are weakened by increasing the number of multiple bonds per uranium cation. We anticipate these results will have broad applications in the fields of organometallic catalysis and nuclear fuels processing. Physical sciences/Chemistry Physical sciences/Chemistry/Coordination chemistry Full Text Additional Declarations There is NO Competing Interest. Supplementary Files EJC05177Et2OPent0m2025.pdf checkcif EJC05177Et2OPent0m2025.cif crystallographic information file nha59sq2025.pdf checkcif PentaimidoSIFINAL.docx Supporting Information nha59sq2025.cif crystallographic information file Cite Share Download PDF Status: Under Review Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-7967522","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":598075075,"identity":"528bb4cd-5b86-46bf-8684-b38dbd4e0882","order_by":0,"name":"Suzanne 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Tetraanion","fulltext":[],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":false,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":true,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":true,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"nature-portfolio","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"","title":"Nature Portfolio","twitterHandle":"","acdcEnabled":false,"dfaEnabled":false,"editorialSystem":"ejp","reportingPortfolio":"","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"","lastPublishedDoi":"10.21203/rs.3.rs-7967522/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-7967522/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eMetal-imido species, those featuring metal-nitrogen multiple bonds M=NR, are common in organometallic chemistry as intermediates in homogeneous catalytic transformations and for supporting highly oxidized non-oxo metal cations.\u003csup\u003e1\u003c/sup\u003e Those featuring multiple imido groups, especially three\u003csup\u003e2-6\u003c/sup\u003e or four,\u003csup\u003e7,8\u003c/sup\u003e are rare reflecting their difficult synthesis and ability of a single metal ion to support the increased π loading. Here, we show the synthesis, isolation, and characterization of the first pentakis(imido) derivative for any metal, the pentakis(imido)uranate(VI) tetra(anion), (K-Et\u003csub\u003e2\u003c/sub\u003eO)\u003csub\u003e4\u003c/sub\u003e[U(NDIPP)\u003csub\u003e5\u003c/sub\u003e]. This species features five terminal uranium-nitrogen multiple bonds with four intercalated potassium cations forcing a geometry that is between trigonal bipyramidal and square pyramidal (t = 0.51). Density functional theory calculations and chemical bonding analysis estimate the U-N bond orders range from 1.5 to 2.0. These values are significantly lower than for previously reported uranium(VI) tris(imido) species\u003csup\u003e9,10\u003c/sup\u003e and tetrakis(imido)uranate(VI) dianions,\u003csup\u003e7\u003c/sup\u003e supporting the hypothesis that strong U-N multiple bonds are weakened by increasing the number of multiple bonds per uranium cation. We anticipate these results will have broad applications in the fields of organometallic catalysis and nuclear fuels processing.\u003c/p\u003e","manuscriptTitle":"Isolation and Characterization of a Pentakis(imido)uranate(VI) Tetraanion","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2026-03-02 08:12:04","doi":"10.21203/rs.3.rs-7967522/v1","editorialEvents":[],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"nature-chemistry","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"nchem","sideBox":"Learn more about [Nature Chemistry](http://www.nature.com/nchem/)","snPcode":"","submissionUrl":"","title":"Nature Chemistry","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"ejp","reportingPortfolio":"Nature Research","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"9436bef7-c421-49c7-a351-afada6176d35","owner":[],"postedDate":"March 2nd, 2026","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"under-review","subjectAreas":[{"id":63644522,"name":"Physical sciences/Chemistry"},{"id":63644523,"name":"Physical sciences/Chemistry/Coordination chemistry"}],"tags":[],"updatedAt":"2026-03-26T10:58:01+00:00","versionOfRecord":[],"versionCreatedAt":"2026-03-02 08:12:04","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-7967522","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-7967522","identity":"rs-7967522","version":["v1"]},"buildId":"XKTyCvWXoU3ODBz1xrDgd","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}