{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,28]],"date-time":"2026-09-28T14:11:38Z","timestamp":1790604698299,"version":"4.1.0"},"reference-count":32,"publisher":"American Chemical Society (ACS)","issue":"38","license":[{"start":{"date-parts":[[2026,9,17]],"date-time":"2026-09-17T00:00:00Z","timestamp":1789603200000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-029"},{"start":{"date-parts":[[2026,9,17]],"date-time":"2026-09-17T00:00:00Z","timestamp":1789603200000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-037"},{"start":{"date-parts":[[2026,9,17]],"date-time":"2026-09-17T00:00:00Z","timestamp":1789603200000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-045"}],"funder":[{"DOI":"10.13039\/100000052","name":"NIH Office of the Director","doi-asserted-by":"publisher","award":["S10OD024998"],"award-info":[{"award-number":["S10OD024998"]}],"id":[{"id":"10.13039\/100000052","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100000015","name":"U.S. Department of Energy","doi-asserted-by":"publisher","award":["DE-AC02-05CH11231"],"award-info":[{"award-number":["DE-AC02-05CH11231"]}],"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-NA0003996"],"award-info":[{"award-number":["DE-NA0003996"]}],"id":[{"id":"10.13039\/100000015","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,9,28]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>While PPh3 is a dominant ligand in transition-metal chemistry, it is completely absent in rare-earth and actinide structural chemistry. The open coordination site and high Lewis acidity of (CpSiMe3)3U are leveraged to generate the first structurally characterized PPh3 complex in these series. X-ray crystallography and variable-temperature nuclear magnetic resonance spectroscopy give insight into the structure and fluxional behavior of (CpSiMe3)3U\u2013PPh3 (1). The U\u2013P bonding energetics were experimentally determined to be endergonic at room temperature, partially rationalizing the absence of triphenylphosphine in f-element chemistry. The structural and dynamic properties of 1 were compared to an analogous phosphite complex, (CpSiMe3)3U\u2013P(OCH2)3CEt (2), and the large discrepancies discussed in the context of \u03c0-bonding and steric interactions.<\/jats:p>","DOI":"10.1021\/acs.inorgchem.6c02892","type":"journal-article","created":{"date-parts":[[2026,9,17]],"date-time":"2026-09-17T06:02:03Z","timestamp":1789624923000},"page":"22209-22213","source":"Crossref","is-referenced-by-count":0,"title":["At the Edge\nof Stability: the Unexpected Isolation\nof an f-Element Triphenylphosphine Complex"],"prefix":"10.1021","volume":"65","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-5485-8991","authenticated-orcid":true,"given":"I. Joseph","family":"Brackbill","sequence":"first","affiliation":[{"name":"University of California , , , ,","place":["Berkeley, California, United States, 94720-1460"]},{"name":"Lawrence Berkeley National Laboratory , , , ,","place":["Berkeley, California, United States, 94720-1460"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9671-227X","authenticated-orcid":true,"given":"John","family":"Arnold","sequence":"additional","affiliation":[{"name":"University of California , , , ,","place":["Berkeley, California, United States, 94720-1460"]},{"name":"Lawrence Berkeley National Laboratory , , , ,","place":["Berkeley, California, United States, 94720-1460"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,9,17]]},"reference":[{"key":"2026092809221198600_cit1","doi-asserted-by":"publisher","first-page":"2784","DOI":"10.1021\/ja01473a054","article-title":"Carbonyl and Hydrido-Carbonyl Complexes of Iridium\nby Reaction with Alcohols. Hydrido Complexes by Reaction with Acid","volume":"83","author":"Vaska","year":"1961","journal-title":"J. Am. Chem. Soc."},{"key":"2026092809221198600_cit2","doi-asserted-by":"publisher","first-page":"1711","DOI":"10.1039\/j19660001711","article-title":"The Preparation\nand Properties of Tris(Triphenylphosphine)Halogenorhodium(I) and Some\nReactions Thereof Including Catalytic Homogeneous Hydrogenation of\nOlefins and Acetylenes and Their Derivatives","author":"Osborn","year":"1966","journal-title":"J. Chem. Soc. A: Inorg., Phys., Theor."},{"key":"2026092809221198600_cit3","doi-asserted-by":"publisher","first-page":"171","DOI":"10.1107\/S2052520616003954","article-title":"The Cambridge Structural\nDatabase","volume":"72","author":"Groom","year":"2016","journal-title":"Acta Crystallogr. Sect. B: Struct.\nSci., Crystal Eng. Mater."},{"key":"2026092809221198600_cit4","doi-asserted-by":"publisher","first-page":"137","DOI":"10.1016\/0010-8545(90)80063-Y","article-title":"Complexes of Groups\n3, 4, the Lanthanides\nand the Actinides Containing Neutral Phosphorus Donor Ligands","volume":"99","author":"Fryzuk","year":"1990","journal-title":"Coordination Chemistry Reviews"},{"key":"2026092809221198600_cit5","doi-asserted-by":"publisher","first-page":"5791","DOI":"10.1021\/ja01507a008","article-title":"The Basicity of\nPhosphines","volume":"82","author":"Henderson","year":"1960","journal-title":"J.\nAm. Chem. Soc."},{"key":"2026092809221198600_cit6","doi-asserted-by":"publisher","first-page":"313","DOI":"10.1021\/cr60307a002","article-title":"Steric\nEffects of Phosphorus Ligands in Organometallic Chemistry and Homogeneous\nCatalysis","volume":"77","author":"Tolman","year":"1977","journal-title":"Chem. Rev."},{"key":"2026092809221198600_cit7","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.202400546","article-title":"Insights Into\nthe Uranium Phosphine Bonds in [UCp3(PR3)]:\nA Combined Molecular Orbital, QTAIM and EDA-NOCV Study","volume":"27","author":"Vondung","year":"2024","journal-title":"Eur. J. Inorg. Chem."},{"key":"2026092809221198600_cit8","doi-asserted-by":"publisher","first-page":"2956","DOI":"10.1021\/ja00713a007","article-title":"Phosphorus\nLigand Exchange Equilibriums on Zerovalent Nickel. Dominant Role for\nSteric Effects","volume":"92","author":"Tolman","year":"1970","journal-title":"J. Am. Chem. Soc."},{"key":"2026092809221198600_cit9","doi-asserted-by":"publisher","first-page":"7792","DOI":"10.1021\/ja00416a019","article-title":"Tertiary Phosphine\nDerivatives of\nthe F-Block Metals. Preparation of X4M(Me2PCH2CH2PMe2)2, Where X Is Halide,\nMethyl or Phenoxy and M Is Thorium or Uranium. Crystal Structure of\nTetraphenoxybis[Bis(1,2-Dimethylphosphino)Ethane]Uranium(IV)","volume":"103","author":"Edwards","year":"1981","journal-title":"J. Am. Chem. Soc."},{"key":"2026092809221198600_cit10","doi-asserted-by":"publisher","first-page":"1038","DOI":"10.1107\/S0108270185006497","article-title":"Structure of Tris(\u03b7-Methylcyclopentadienyl)(Trimethylphosphine)Uranium(III),\n[U(CH3C5H4)3{P(CH3)3}]","volume":"41","author":"Brennan","year":"1985","journal-title":"Acta Crystallographica\nSection C: Crystal Structure Communications"},{"key":"2026092809221198600_cit11","volume-title":"Organoactinide Chemistry:\nSynthesis, Structure, and Solution Dynamics","author":"Brennan","year":"1986"},{"key":"2026092809221198600_cit12","doi-asserted-by":"publisher","first-page":"201","DOI":"10.1016\/S0020-1693(00)84079-7","article-title":"The Coordination Chemistry\nof Trivalent Uranium and Cerium","volume":"139","author":"Brennan","year":"1987","journal-title":"Inorganica\nChimica Acta"},{"key":"2026092809221198600_cit13","doi-asserted-by":"publisher","first-page":"4162","DOI":"10.1021\/acs.inorgchem.1c00327","article-title":"Instantaneous and\nPhosphine-Catalyzed Arene Binding and Reduction by U(III) Complexes","volume":"60","author":"Arnold","year":"2021","journal-title":"Inorg. Chem."},{"key":"2026092809221198600_cit14","doi-asserted-by":"publisher","first-page":"1913","DOI":"10.1021\/jacs.8b13514","article-title":"Million-Fold Relaxation\nTime Enhancement\nacross a Series of Phosphino-Supported Erbium Single-Molecule Magnets","volume":"141","author":"Hilgar","year":"2019","journal-title":"J. Am. Chem. Soc."},{"key":"2026092809221198600_cit15","doi-asserted-by":"publisher","first-page":"412","DOI":"10.1016\/S0022-328X(00)80334-4","article-title":"Innere Elektronenanregungen von Tricyclopentadienyl-Komplexen\nDes Ytterbiums","volume":"4","author":"Fischer","year":"1965","journal-title":"Journal of Organometallic Chemistry"},{"key":"2026092809221198600_cit16","doi-asserted-by":"publisher","first-page":"141","DOI":"10.1016\/S0022-328X(00)93649-0","article-title":"Komplexe von Lanthaniden-Tricyclopentadienylen\nMit\nBasen","volume":"6","author":"Fischer","year":"1966","journal-title":"Journal of Organometallic Chemistry"},{"key":"2026092809221198600_cit17","doi-asserted-by":"publisher","first-page":"21932","DOI":"10.1021\/jacs.4c06777","article-title":"Covalency-Driven Differences in the\nHydrogenation Chemistry of Lanthanide- and Actinide-Based Frustrated\nLewis Pairs","volume":"146","author":"Brackbill","year":"2024","journal-title":"J. Am. Chem. Soc."},{"key":"2026092809221198600_cit18","doi-asserted-by":"publisher","first-page":"13767","DOI":"10.1021\/ja904565j","article-title":"A Comparison of 4f\nvs 5f Metal-Metal Bonds in (CpSiMe3)3M-ECp*\n(M = Nd, U; E = Al, Ga; Cp* = C5Me5): Synthesis,\nThermodynamics, Magnetism, and Electronic Structure","volume":"131","author":"Minasian","year":"2009","journal-title":"J. Am. Chem. Soc."},{"key":"2026092809221198600_cit19","doi-asserted-by":"publisher","first-page":"2360","DOI":"10.1002\/chem.202000214","article-title":"Synthesis and Structure of Uranium-Silylene Complexes","volume":"26","author":"Brackbill","year":"2020","journal-title":"Chem.\u2013Eur. J."},{"key":"2026092809221198600_cit20","unstructured":"PPh3 did not demonstrate\nthis behavior in the absence of (CpSiMe3)3U.\nSee the Supporting Information for this and other VT NMR data."},{"key":"2026092809221198600_cit21","doi-asserted-by":"publisher","first-page":"53","DOI":"10.1016\/0022-328X(92)83484-Y","article-title":"Anionic Triscyclopentadienyluranium(III)\nHydrides","volume":"440","author":"Berthet","year":"1992","journal-title":"J. Organomet. Chem."},{"key":"2026092809221198600_cit22","doi-asserted-by":"publisher","first-page":"335","DOI":"10.1016\/0022-328X(91)83205-I","article-title":"Synthesis\nand Crystal Structure of\nthe Oxo-Bridged Bimetallic Organouranium Complex [(Me3SiC5H4)3U]2[\u03bc-O]","volume":"408","author":"Berthet","year":"1991","journal-title":"J. Organomet. Chem."},{"key":"2026092809221198600_cit23","doi-asserted-by":"publisher","first-page":"12620","DOI":"10.1039\/D0CC06044E","article-title":"Polarised Covalent Thorium(IV)\u2013\nand Uranium(IV)\u2013Silicon Bonds","volume":"56","author":"Re\u0301ant","year":"2020","journal-title":"Chem.\nCommun."},{"key":"2026092809221198600_cit24","doi-asserted-by":"publisher","first-page":"772","DOI":"10.1002\/chem.201503583","article-title":"Expanding\nthe Chemistry of Molecular U2+ Complexes: Synthesis, Characterization,\nand Reactivity of the [C5H3(SiMe3)2]3U- Anion. Chem.\u2013","volume":"22","author":"Windorff","year":"2016","journal-title":"Eur. J."},{"key":"2026092809221198600_cit25","doi-asserted-by":"publisher","first-page":"1329","DOI":"10.1021\/om00096a016","article-title":"Crystal Structures\nof (MeC5H4)3ML [M = Uranium or Cerium;\nL = Quinuclidine or P(OCH2)3CEt]. Evidence for\nUranium to Phosphorus \u03c0-Back-Bonding","volume":"7","author":"Brennan","year":"1988","journal-title":"Organometallics"},{"key":"2026092809221198600_cit26","doi-asserted-by":"publisher","first-page":"1706","DOI":"10.1107\/S0108270187090474","article-title":"\u03bc-[Ethylenebis(Dimethylphosphine)]-Bis[Tris(Cyclopentadienyl)Uranium(IV)]","volume":"43","author":"Zalkin","year":"1987","journal-title":"Acta Crystallographica Section C"},{"key":"2026092809221198600_cit27","doi-asserted-by":"publisher","first-page":"3629","DOI":"10.1021\/om801098b","article-title":"The Bond between CO and Cp\u20323U in\nCp\u20323U(CO) Involves Back-bonding from\nthe Cp\u20323U Ligand-Based Orbitals of \u03c0-Symmetry, Where Cp\u2032 Represents a Substituted Cyclopentadienyl\nLigand","volume":"28","author":"Maron","year":"2009","journal-title":"Organometallics"},{"key":"2026092809221198600_cit28","doi-asserted-by":"publisher","first-page":"11508","DOI":"10.1039\/C6DT00634E","article-title":"The Roles of 4f- and 5f-Orbitals in Bonding: A Magnetochemical,\nCrystal Field, Density Functional Theory, and Multi-Reference Wavefunction\nStudy","volume":"45","author":"Lukens","year":"2016","journal-title":"Dalton Transactions"},{"key":"2026092809221198600_cit29","doi-asserted-by":"publisher","first-page":"579","DOI":"10.1039\/B313992A","article-title":"Lanthanide(III)\/Actinide(III)\nDifferentiation in Coordination of Azine Molecules to Tris(Cyclopentadienyl)\nComplexes of Cerium and Uranium","volume":"0","author":"Mehdoui","year":"2004","journal-title":"Dalton Transactions"},{"key":"2026092809221198600_cit30","doi-asserted-by":"publisher","first-page":"2104","DOI":"10.1107\/S0108270188008327","article-title":"Tris(Trimethylsilylcyclopentadienyl)Uranium(III)","volume":"44","author":"Zalkin","year":"1988","journal-title":"Acta Crystallographica Section C: Crystal Structure Communications"},{"key":"2026092809221198600_cit31","doi-asserted-by":"publisher","first-page":"1517","DOI":"10.1016\/S0277-5387(00)81779-9","article-title":"A New Approach to\nMeasuring Absolute Metal\u2500Ligand Bond Disruption Enthalpies\nin Organometallic Compounds. The [(CH3)3SiC5H4]3U-system","volume":"7","author":"Schock","year":"1988","journal-title":"Polyhedron"},{"key":"2026092809221198600_cit32","doi-asserted-by":"publisher","first-page":"5075","DOI":"10.1021\/ja00511a054","article-title":"Pentamethylcyclopentadienyl Organoactinides. Trivalent\nUranium Organometallic Chemistry and the Unusual Structure of Bis(Pentamethylcyclopentadienyl)Uranium\nMonochloride","volume":"101","author":"Manriquez","year":"1979","journal-title":"J. Am. Chem. Soc."}],"container-title":["Inorganic Chemistry"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/acs.inorgchem.6c02892","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/inocaj\/article-pdf\/65\/38\/22209\/68539492\/acs.inorgchem.6c02892.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/inocaj\/article-pdf\/65\/38\/22209\/68539492\/acs.inorgchem.6c02892.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,9,28]],"date-time":"2026-09-28T13:32:18Z","timestamp":1790602338000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/inocaj\/article\/65\/38\/22209\/5431762\/At-the-Edge-of-Stability-the-Unexpected-Isolation"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,9,17]]},"references-count":32,"journal-issue":{"issue":"38","published-online":{"date-parts":[[2026,9,17]]},"published-print":{"date-parts":[[2026,9,28]]}},"URL":"https:\/\/doi.org\/10.1021\/acs.inorgchem.6c02892","relation":{},"ISSN":["0020-1669","1520-510X"],"issn-type":[{"value":"0020-1669","type":"print"},{"value":"1520-510X","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,9,17]]}}}