Despite there being numerous examples of f‐element compounds supported by cyclopentadienyl, arene, cycloheptatrienyl, and cyclooctatetraenyl ligands (C5–8), cyclobutadienyl (C4) complexes remain exceedingly rare. Here, we report that reaction of [Li2{C4(SiMe3)4}(THF)2] (1) with [U(BH4)3(THF)2] (2) gives the pianostool complex [U{C4(SiMe3)4}(BH4)3][Li(THF)4] (3), where use of a borohydride and preformed C4‐unit circumvents difficulties in product isolation and closing a C4‐ring at uranium. Complex 3 is an unprecedented example of an f‐element half‐sandwich cyclobutadienyl complex, and it is only the second example of an actinide‐cyclobutadienyl complex, the other being an inverse‐sandwich. The U−C distances are short (av. 2.513 Å), reflecting the formal 2− charge of the C4‐unit, and the SiMe3 groups are displaced from the C4‐plane, which we propose maximises U−C4 orbital overlap. DFT calculations identify two quasi‐degenerate U−C4 π‐bonds utilising the ψ2 and ψ3 molecular orbitals of the C4‐unit, but the potential δ‐bond using the ψ4 orbital is vacant.
Determining the nature and extent of covalency of early actinide chemical bonding is a fundamentally important challenge. Recently, X-ray absorption, electron paramagnetic, and nuclear magnetic resonance spectroscopic studies have probed actinide-ligand covalency, largely confirming the paradigm of early actinide bonding varying from ionic to polarised-covalent, with this range sitting on the continuum between ionic lanthanide and more covalent d transition metal analogues. Here, we report measurement of the covalency of a terminal uranium(VI)-nitride by 15N nuclear magnetic resonance spectroscopy, and find an exceptional nitride chemical shift and chemical shift anisotropy. This redefines the 15N nuclear magnetic resonance spectroscopy parameter space, and experimentally confirms a prior computational prediction that the uranium(VI)-nitride triple bond is not only highly covalent, but, more so than d transition metal analogues. These results enable construction of general, predictive metal-ligand 15N chemical shift-bond order correlations, and reframe our understanding of actinide chemical bonding to guide future studies.
Neutral mesoionic carbenes (MICs) have emerged as an important class of carbene, however they are found in the free form or ligated to only a few d‐block ions. Unprecedented f‐block MIC complexes [M(N′′)3{CN(Me)C(Me)N(Me)CH}] (M=U, Y, La, Nd; N′′=N(SiMe3)2) are reported. These complexes were prepared by a formal 1,4‐proton migration reaction when the metal triamides [M(N′′)3] were treated with the N‐heterocyclic olefin H2C=C(NMeCH)2, which constitutes a new, general way to prepare MIC complexes. Quantum chemical calculations on the 5f3 uranium(III) complex suggest the presence of a U=C donor‐acceptor bond, composed of a MIC→U σ‐component and a U(5f)→MIC(2p) π‐back‐bond, but for the d0f0 Y and La and 4f3 Nd congeners only MIC→M σ‐bonding is found. Considering the generally negligible π‐acidity of MICs, this is surprising and highlights that greater consideration should possibly be given to recognizing MICs as potential π‐acid ligands when coordinated to strongly reducing metals.
Reaction of [Li 2 {C 4 (SiMe 3 ) 4 }(THF) 2 ] (1) with [U(η 5 -C 5 Me 5 )I 2 (THF)] (2) produced the oxo-centered homotrimetallic uranium−pentamethylcyclopentadienyl complex [{U(η 5 -C 5 Me 5 )(μ-I) 2 } 3 {μ 3 -O}{Li(THF) 3 } 0.5 ] 2 [Li(THF) 4 ] (3) as the only isolable product in a very low yield. In contrast, reaction of 2 with [Mg{C 4 (SiMe 3 ) 4 }(THF) 3 ] (4) produced the oxo-centered homotrimetallic uranium(IV)−cyclobutadienyl complex [{U(C 4 [SiMe 3 ] 4 )(μ-I) 2 } 3 {μ 3 -O}][Mg(THF) 6 ] (5). The solid state structure of 5 reveals average U−C and U−C 4 centroid distances of 2.574( 7) and 2.355(7) Å, respectively, and displacements of the silicon atoms from the C 4 plane ranging from 0.478(13) to 0.6528(12) Å. Variable-temperature magnetic susceptibility measurements on powdered 5 confirm the exclusively uranium(IV) formulation with no evidence found for any uranium•••uranium magnetic coupling. Quantum chemical calculations suggest polarized uranium−cyclobutadienyl bonding interactions but underscore the essentially exclusive π-bonding nature of these linkages with no δ-bonding component. This π-bonding also accounts for the displacements of the silyl groups from the C 4 plane, which maximizes U−C 4 orbital overlap. The compounds reported here have been variously characterized by single-crystal X-ray diffraction, ATR-IR spectroscopy, elemental analysis, SQUID magnetometry, and quantum chemical calculations.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.