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The reduction chemistry of the newly emerging 2‐phosphaethynolate (OCP)− is not well explored, and many unanswered questions remain about this ligand in this context. We report that reduction of [Th(TrenTIPS)(OCP)] (2, TrenTIPS=[N(CH2CH2NSiPri3)]3−), with RbC8 via [2+2+1] cycloaddition, produces an unprecedented hexathorium complex [{Th(TrenTIPS)}6(μ‐OC2P3)2(μ‐OC2P3H)2Rb4] (5) featuring four five‐membered [C2P3] phosphorus heterocycles, which can be converted to a rare oxo complex [{Th(TrenTIPS)(μ‐ORb)}2] (6) and the known cyclometallated complex [Th{N(CH2CH2NSiPri3)2(CH2CH2SiPri2CHMeCH2)}] (4) by thermolysis; thereby, providing an unprecedented example of reductive cycloaddition reactivity in the chemistry of 2‐phosphaethynolate. This has permitted us to isolate intermediates that might normally remain unseen. We have debunked an erroneous assumption of a concerted fragmentation process for (OCP)−, rather than cycloaddition products that then decompose with [Th(TrenTIPS)O]− essentially acting as a protecting then leaving group. In contrast, when KC8 or CsC8 were used the phosphinidiide C−H bond activation product [{Th(TrenTIPS)}Th{N(CH2CH2NSiPri3)2[CH2CH2SiPri2CH(Me)CH2C(O)μ‐P]}] (3) and the oxo complex [{Th(TrenTIPS)(μ‐OCs)}2] (7) were isolated. [ABSTRACT FROM AUTHOR]

Treatment of [Ph3EMe][I] with [Na{N(SiMe3)2}] affords the ylides [Ph3E=CH2] (E=As, 1As; P, 1P). For 1As this overcomes prior difficulties in the synthesis of this classical arsonium‐ylide that have historically impeded its wider study. The structure of 1As has now been determined, 45 years after it was first convincingly isolated, and compared to 1P, confirming the long‐proposed hypothesis of increasing pyramidalisation of the ylide‐carbon, highlighting the increasing dominance of E+−C− dipolar resonance form (sp3‐C) over the E=C ene π‐bonded form (sp2‐C), as group 15 is descended. The uranium(IV)–cyclometallate complex [U{N(CH2CH2NSiPri3)2(CH2CH2SiPri2CH(Me)CH2)}] reacts with 1As and 1P by α‐proton abstraction to give [U(TrenTIPS)(CHEPh3)] (TrenTIPS=N(CH2CH2NSiPri3)3; E=As, 2As; P, 2P), where 2As is an unprecedented structurally characterised arsonium‐carbene complex. The short U−C distances and obtuse U‐C‐E angles suggest significant U=C double bond character. A shorter U−C distance is found for 2As than 2P, consistent with increased uranium‐ and reduced pnictonium‐stabilisation of the carbene as group 15 is descended, which is supported by quantum chemical calculations. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Reaction of [U{C(SiMe3)(PPh2)}(BIPM)(m-Cl)Li-(TMEDA)(m-TMEDA)0.5]2 (BIPM=C(PPh2NSiMe3)2; TMEDA=Me2NCH2CH2NMe2) with [Rh(m-Cl)(COD)]2 (COD=cyclooctadiene) affords the heterotrimetallic UIV@ Rh2I complex [U(Cl)2{C(PPh2NSiMe3)(PPh[C6H4]NSiMe3)}-{Rh(COD)}{Rh(CH(SiMe3)(PPh2)}]. This complex has a very short uranium-rhodium distance, the shortest uranium-rhodium bond on record and the shortest actinide-transition metal bond in terms of formal shortness ratio. Quantum-chemical calculations reveal a remarkable RhI⇉UIV net double dative bond interaction, involving RhI 4dz2- and 4dxy/xz-type donation into vacant UIV 5f orbitals, resulting in a Wiberg/Nalewajski-Mrozek U-Rh bond order of 1.30/1.44, respectively. Despite being, formally, purely dative, the uranium-rhodium bonding interaction is the most substantial actinide-metal multiple bond yet prepared under conventional experimental conditions, as confirmed by structural, magnetic, and computational analyses. [ABSTRACT FROM AUTHOR]

Abstract: The synthesis and characterisation is presented of the compounds [An(TrenDMBS){Pn(SiMe3)2}] and [An(TrenTIPS){Pn(SiMe3)2}] [TrenDMBS=N(CH2CH2NSiMe2But)3, An=U, Pn=P, As, Sb, Bi; An=Th, Pn=P, As; TrenTIPS=N(CH2CH2NSiPri3)3, An=U, Pn=P, As, Sb; An=Th, Pn=P, As, Sb]. The U−Sb and Th−Sb moieties are unprecedented examples of any kind of An−Sb molecular bond, and the U−Bi bond is the first two‐centre‐two‐electron (2c–2e) one. The Th−Bi combination was too unstable to isolate, underscoring the fragility of these linkages. However, the U−Bi complex is the heaviest 2c–2e pairing of two elements involving an actinide on a macroscopic scale under ambient conditions, and this is exceeded only by An−An pairings prepared under cryogenic matrix isolation conditions. Thermolysis and photolysis experiments suggest that the U−Pn bonds degrade by homolytic bond cleavage, whereas the more redox‐robust thorium compounds engage in an acid–base/dehydrocoupling route. [ABSTRACT FROM AUTHOR]

Reaction of [U(TrenTIPS)] [ 1, TrenTIPS=N(CH2CH2NSi iPr3)3] with 0.25 equivalents of P4 reproducibly affords the unprecedented actinide inverted sandwich cyclo-P5 complex [{U(TrenTIPS)}2(μ-η5:η5-cyclo-P5)] ( 2). All prior examples of cyclo-P5 are stabilized by d-block metals, so 2 shows that cyclo-P5 does not require d-block ions to be prepared. Although cyclo-P5 is isolobal to cyclopentadienyl, which usually bonds to metals via σ- and π-interactions with minimal δ-bonding, theoretical calculations suggest the principal bonding in the U(P5)U unit is polarized δ-bonding. Surprisingly, the characterization data are overall consistent with charge transfer from uranium to the cyclo-P5 unit to give a cyclo-P5 charge state that approximates to a dianionic formulation. This is ascribed to the larger size and superior acceptor character of cyclo-P5 compared to cyclopentadienyl, the strongly reducing nature of uranium(III), and the availability of uranium δ-symmetry 5f orbitals. [ABSTRACT FROM AUTHOR]