A Uranium(VI)-Oxo-Imido Dimer Complex Derived from a Sterically Demanding Triamidoamine.

The reaction of [UO2(µ-Cl)4{K(18-crown-6)}2] with [{N(CH2CH2NSiPri3)3}Li3] gives [{UO(µ-NCH2CH2N[CH2CH2NSiPri3]2)}2] (1), [{(LiCl)(KCl)(18-crown-6)}2] (2), and [LiOSiPri3] (3) in a 1:2:2 ratio. The formation of the oxo-imido 1 involves the cleavage of a N-Si bond and the activation of one of the usually robust U═O bonds of uranyl(VI), resulting in the formation of uranium(VI)-imido and siloxide linkages. Notably, the uranium oxidation state remains unchanged at +6 in the starting material and product. Structural characterization suggests the dominance of a core RN═U═O group, and the dimeric formulation of 1 is supported by bridging imido linkages in a highly asymmetric U2N2 ring. Density functional theory analyses find a σ > π orbital energy ordering for the U═N and U═O bonds in 1, which is uranyl-like in nature. Complexes 1-3 were characterized variously by single crystal X-ray diffraction, multinuclear NMR, IR, Raman, and optical spectroscopies; cyclic voltammetry; and density functional theory.

Uranyl-tri- bis(silyl)amide Alkali Metal Contact and Separated Ion Pair Complexes.

We report the preparation of a range of alkali metal uranyl(VI) tri- bis(silyl)amide complexes [{M(THF) x}{(µ-O)U(O)(N″)3}] (1M) (N″ = {N(SiMe3)2}-, M = Li, Na, x = 2; M = K, x = 3; M = K, Rb, Cs, x = 0) containing electrostatic alkali metal uranyl-oxo interactions. Reaction of 1M with 2,2,2-cryptand or 2 equiv of the appropriate crown ether resulted in the isolation of the separated ion pair species [U(O)2(N″)3][M(2,2,2-cryptand)] (3M, M = Li-Cs) and [U(O)2(N″)3][M(crown)2] (4M, M = Li, crown = 12-crown-4 ether; M = Na-Cs, crown = 15-crown-5 ether). A combination of crystallographic studies and IR, Raman and UV-vis spectroscopies has revealed that the 1M series adopts contact ion pair motifs in the solid state where the alkali metal caps one of the uranyl-oxo groups. Upon dissolution in THF solution, this contact is lost, and instead, separated ion pair motifs are observed, which is confirmed by the isolation of [U(O)2(N″)3][M(THF) n] (2M) (M = Li, n = 4; M = Na, K, n = 6). The compounds have been characterized by single crystal X-ray diffraction, multinuclear NMR spectroscopy, IR, Raman, and UV-vis spectroscopies, and elemental analyses.

A Very Short Uranium(IV)-Rhodium(I) Bond with Net Double-Dative Bonding Character.

Reaction of [U{C(SiMe3 )(PPh2 )}(BIPM)(µ-Cl)Li(TMEDA)(µ-TMEDA)0.5 ]2 (BIPM=C(PPh2 NSiMe3 )2 ; TMEDA=Me2 NCH2 CH2 NMe2 ) with [Rh(µ-Cl)(COD)]2 (COD=cyclooctadiene) affords the heterotrimetallic UIV -RhI2 complex [U(Cl)2 {C(PPh2 NSiMe3 )(PPh[C6 H4 ]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.

Correction: f-Element heavy pnictogen chemistry.

[This corrects the article DOI: 10.1039/D3SC05056D.].

Metal-carbon bonding in early lanthanide substituted cyclopentadienyl complexes probed by pulsed EPR spectroscopy.

We examine lanthanide (Ln)-ligand bonding in a family of early Ln3+ complexes [Ln(Cptt)3] (1-Ln, Ln = La, Ce, Nd, Sm; Cptt = C5H3tBu2-1,3) by pulsed electron paramagnetic resonance (EPR) methods, and provide the first characterization of 1-La and 1-Nd by single crystal XRD, multinuclear NMR, IR and UV/Vis/NIR spectroscopy. We measure electron spin T1 and Tm relaxation times of 12 and 0.2 µs (1-Nd), 89 and 1 µs (1-Ce) and 150 and 1.7 µs (1-Sm), respectively, at 5 K: the T1 relaxation of 1-Nd is more than 102 times faster than its valence isoelectronic uranium analogue. 13C and 1H hyperfine sublevel correlation (HYSCORE) spectroscopy reveals that the extent of covalency is negligible in these Ln compounds, with much smaller hyperfine interactions than observed for equivalent actinide (Th and U) complexes. This is corroborated by ab initio calculations, confirming the predominant electrostatic nature of the metal-ligand bonding in these complexes.

f-Element heavy pnictogen chemistry.

The coordination and organometallic chemistry of the f-elements, that is group 3, lanthanide, and actinide ions, supported by nitrogen ligands, e.g. amides, imides, and nitrides, has become well developed over many decades. In contrast, the corresponding f-element chemisty with the heavier pnictogen analogues phosphorus, arsenic, antimony, and bismuth has remained significantly underdeveloped, due largely to a lack of suitable synthetic methodologies and also the inherent hard(f-element)-soft(heavier pnictogen) acid-base mismatch, but has begun to flourish in recent years. Here, we review complexes containing chemical bonds between the f-elements and heavy pnictogens from phosphorus to bismuth that spans five decades of endeavour. We focus on complexes whose identity has been unambiguously established by structural authentication by single-crystal X-ray diffraction with respect to their synthesis, characterisation, bonding, and reactivity, in order to provide a representative overview of this burgeoning area. By highlighting that much has been achieved but that there is still much to do this review aims to inspire, focus and guide future efforts in this area.

Synthesis and characterisation of light lanthanide bis-phospholyl borohydride complexes.

Organometallic lanthanide (Ln) chemistry is dominated by complexes that contain substituted cyclopentadienyl (CpR) ligands. Closely related phospholyls have received less attention, and although they have proven utility in stabilising low oxidation state Ln complexes the trivalent Ln chemistry of these ligands is limited in comparison. Herein, we synthesise two families of heteroleptic Ln3+ complexes, [Ln(Htp)2(µ-BH4)]2 (Htp = 2,5-di-tert-butylphospholyl; 1-Ln; Ln = La, Ce, Nd, Sm), and [[Ln(Htp)2(µ-BH4)2K(S)]n (2-Ln, Ln = La, Ce, S = 2 DME, n = 2; 3-Ce, Ln = Ce, S = Et2O and THF, n = ∞) via the reactions of parent [Ln(BH4)3(THF)3.5] with K(Htp), to investigate differences between Ln complexes with substituted phospholyl ligands and analogous CpR complexes. Complexes 1-3-Ln were characterised as appropriate by single crystal XRD, SQUID magnetometry, elemental analysis, multinuclear NMR, ATR-IR and UV-Vis-NIR spectroscopy. Ab initio calculations reveal that small changes in the Ln3+ coordination spheres of these complexes can have relatively large influences on crystal field splitting.

Back-bonding between an electron-poor, high-oxidation-state metal and poor π-acceptor ligand in a uranium(V)-dinitrogen complex.

A fundamental bonding model in coordination and organometallic chemistry is the synergic, donor-acceptor interaction between a metal and a neutral π-acceptor ligand, in which the ligand σ donates to the metal, which π back-bonds to the ligand. This interaction typically involves a metal with an electron-rich, mid-, low- or even negative oxidation state and a ligand with a π* orbital. Here, we report that treatment of a uranium-carbene complex with an organoazide produces a uranium(V)-bis(imido)-dinitrogen complex, stabilized by a lithium counterion. This complex, which was isolated in a crystalline form, involves an electron-poor, high-oxidation-state uranium(V) 5f1 ion that is π back-bonded to the poor π-acceptor ligand dinitrogen. We propose that this is made possible by a combination of cooperative heterobimetallic uranium-lithium effects and the presence of suitable ancillary ligands that render the uranium ion unusually electron rich. This electron-poor back-bonding could have implications for the field of dinitrogen activation.