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Treatment of [U IV(N 3)(Tren TIPS)] (1, Tren TIPS = {N(CH 2CH 2NSiPr i 3) 3} 3−) with excess Li resulted in the isolation of [{U IV(μ-NLi 2)(Tren TIPS)} 2] (2), which exhibits a diuranium(iv) ‘diamond-core’ dinitride motif. Over-reduction of 1 produces [U III(Tren TIPS)] (3), and together with known [{U V(μ-NLi)(Tren TIPS)} 2] (4) an overall reduction sequence 1 → 4 → 2 → 3 is proposed. Attempts to produce an odd-electron nitride from 2 resulted in the formation of [{U IV(Tren TIPS)} 2(μ-NH)(μ-NLi 2)Li] (5). Use of heavier alkali metals did not result in the formation of analogues of 2, emphasising the role of the high charge-to-radius-ratio of lithium stabilising the charge build up at the nitride. Variable-temperature magnetic data for 2 and 5 reveal large low-temperature magnetic moments, suggesting doubly degenerate ground states, where the effective symmetry of the strong crystal field of the nitride dominates over the spin-orbit coupled nature of the ground multiplet of uranium(iv). Spin Hamiltonian modelling of the magnetic data for 2 and 5 suggest U⋯U anti-ferromagnetic coupling of −4.1 and −3.4 cm −1, respectively. The nature of the U⋯U electronic communication was probed computationally, revealing a borderline case where the prospect of direct uranium-uranium bonding was raised, but in-depth computational analysis reveals that if any uranium-uranium bonding is present it is weak, and instead the nitride centres dominate the mediation of U⋯U electronic communication. This highlights the importance of obtaining high-level ab initio insight when probing potential actinide-actinide electronic communication and bonding in weakly coupled systems. The computational analysis highlights analogies between the ‘diamond-core’ dinitride of 2 and matrix-isolated binary U 2N 2

We report magnetic hysteresis studies of three Dy(III) single-molecule magnets (SMMs). The three compounds are [Dy(tBuO)Cl(THF)5][BPh4] (1), [K(18-crown-6-ether)(THF)2][Dy(BIPM)2] (2, BIPM = C{PPh2NSiMe3}2), and [Dy(Cpttt)2][B(C6F5)4] (3), chosen as they have large energy barriers to magnetisation reversal of 665, 565, and 1223 cm-1, respectively. There are zero-field steps in the hysteresis loops of all three compounds, that remain in magnetically dilute samples and in samples that are isotopically enriched with 164Dy, which has no nuclear spin. These results demonstrate that neither dipolar fields nor nuclear hyperfine coupling are solely responsible for the quantum tunnelling of magnetisation at zero field. Analysing their vibrational modes, we find that the modes that most impact the first coordination sphere occur at the lowest energies for 1, at intermediate energies for 2 and at higher energies for 3, in correlation with the hysteresis coercive fields. Therefore, we suggest that the efficiency of quantum tunnelling of magnetisation is related to molecular flexibility.

Treatment of the new methanediide–methanide complex [Dy(SCS)(SCSH)(THF)] (1Dy, SCS = {C(PPh2S)2}2−) with alkali metal alkyls and auxillary ethers produces the bis-methanediide complexes [Dy(SCS)2][Dy(SCS)2(K(DME)2)2] (2Dy), [Dy(SCS)2][Na(DME)3] (3Dy) and [Dy(SCS)2][K(2,2,2-cryptand)] (4Dy). For further comparisons, the bis-methanediide complex [Dy(NCN)2][K(DB18C6)(THF)(toluene)] (5Dy, NCN = {C(PPh2NSiMe3)2}2−, DB18C6 = dibenzo-18-crown-6 ether) was prepared. Magnetic susceptibility experiments reveal slow relaxation of the magnetisation for 2Dy–5Dy, with open magnetic hysteresis up to 14, 12, 15, and 12 K, respectively (∼14 Oe s−1). Fitting the alternating current magnetic susceptibility data for 2Dy–5Dy gives energy barriers to magnetic relaxation (Ueff) of 1069(129)/1160(21), 1015(32), 1109(70), and 757(39) K, respectively, thus 2Dy–4Dy join a privileged group of SMMs with Ueff values of ∼1000 K and greater with magnetic hysteresis at temperatures >10 K. These structurally similar Dy-components permit systematic correlation of the effects of axial and equatorial ligand fields on single-molecule magnet performance. For 2Dy–4Dy, the Dy-components can be grouped into 2Dy–cation/4Dy and 2Dy–anion/3Dy, where the former have almost linear C Created by potrace 1.16, written by Peter Selinger 2001-2019 DyC units with short average DyC distances, and the latter have more bent CDyC units with longer average DyC bonds. Both Ueff and hysteresis temperature are superior for the former pair compared to the latter pair as predicted, supporting the hypothesis that a more linear axial ligand field with shorter M–L distances produces enhanced SMM properties. Comparison with 5Dy demonstrates unusually clear-cut examples of: (i) weakening the equatorial ligand field results in enhancement of the SMM performance of a monometallic system; (ii) a positive correlation between Ueff barrier and axial linearity in structurally comparable systems., Studies on equatorial donor and CDyC angle variation effects on energy barriers to the slow relaxation of magnetisation are reported.

We report unprecedented silyl-phosphino-carbene complexes of uranium(IV), where before all covalent actinide-carbon double bonds were stabilised by phosphorus(V) substituents or restricted to matrix isolation experiments. Conversion of [U(BIPMTMS)(Cl)(μ-Cl)2Li(THF)2] (1, BIPMTMS = C(PPh2NSiMe3)2) to [U(BIPMTMS)(Cl){CH(Ph)(SiMe3)}] (2), and addition of [Li{CH(SiMe3)(PPh2)}(THF)] and Me2NCH2CH2NMe2 (TMEDA) gave [U{C(SiMe3)(PPh2)}(BIPMTMS)(μ-Cl)Li(TMEDA)(μ-TMEDA)0.5]2 (3) by α-hydrogen abstraction. Addition of 2,2,2-cryptand or two equivalents of 4-N,N-dimethylaminopyridine (DMAP) to 3 gave [U{C(SiMe3)(PPh2)}(BIPMTMS)(Cl)][Li(2,2,2-cryptand)] (4) or [U{C(SiMe3)(PPh2)}(BIPMTMS)(DMAP)2] (5). The characterisation data for 3-5 suggest that whilst there is evidence for 3-centre P-C-U π-bonding character, the U=C double bond component is dominant in each case. These U=C bonds are the closest to a 'true' uranium-alkylidene, yet outside of matrix isolation experiments.

Neutral mesoionic carbenes (MICs) have emerged as an important class of carbene, however they are found only in the free form or ligated to a few d-block ions. Here, we report unprecedented f-block MIC complexes [M(N'')3{CN(Me)C(Me)N(Me)CH}] (M = U, Y, La, Nd; N'' = N(SiMe3)2). 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 recognising MICs as potential π-acid ligands when coordinated to reducing metals.

The yttrium methanediide complex [Y(BIPM)(I)(THF)2] (BIPM = {C(PPh2NSiMe3)2}) was reacted with a series of potassium bis(silyl)amides to produce heteroleptic complexes by salt metathesis protocols. The methanediide complexes [Y(BIPM)(N″)(THF)] (1; N″ = {N(SiMe3)2}) and [Y(BIPM)(N**)(THF)] (2; N** = {N(SiMe2tBu)2}) were obtained for those relatively small bis(silyl)amides. Complex 2 undergoes thermal decomposition under vacuum to yield the methanide cyclometalate complex [Y(H-BIPM){N(SitBuMe2)(SitBuMeCH2)-κ2-N,C}] (3) as part of an otherwise intractable mixture of products. Complex 3 was also observed in trace amounts in mixtures of [Y(BIPM)(I)(THF)2] and KN**. In contrast, [Y(BIPM)(I)(THF)2] reacted with the more sterically demanding potassium bis(silyl)amides KN*† (N*† = {N(SiMe2tBu)(SiiPr3)}) and KN†† (N†† = {N(SiiPr3)2}) to afford the methanide cyclometalate complexes [Y(H-BIPM){N(SiiPr3)(SitBuMeCH2)-κ2-N,C)}] (4) and [Y(H-BIPM){N(SiiPr3)[SiiPr2(CHMeCH2)]-κ2-N,C}] (5), respectively. Complexes 1–5 were characterized as appropriate by multinuclear NMR and FTIR spectroscopy, elemental analyses, and single-crystal X-ray diffraction.

Energy barriers to magnetisation reversal (Ueff) in single-molecule magnets (SMMs) have vastly increased recently, but only for the dysprosocenium SMM [Dy(Cpttt)2][B(C6F5)4] (Cpttt = C5H2tBu3-1,2,4) has this translated into a considerable increase in magnetic hysteresis temperatures. The lack of concomitant increases in hysteresis temperatures with Ueff values is due to efficient magnetic relaxation at zero-field, referred to as quantum tunnelling of the magnetisation (QTM); however, the exact nature of this phenomenon is unknown. Recent hypotheses suggest that both transverse dipolar magnetic fields and hyperfine coupling play a significant role in this process for Dy(III) SMMs. Here, by studying the compounds [Dy(tBuO)Cl(THF)5][BPh4] (1), [K(18-crown-6-ether)(THF)2][Dy(BIPM)2] (2, BIPM = C{PPh2NSiMe3}2), and [Dy(Cpttt)2][B(C6F5)4] (3), we show conclusively that neither of these processes are the main contributor to zero-field QTM for Dy(III) SMMs, and suggest that its origin instead owes to molecular flexibility. By analysing the vibrational modes of the three molecules, we show that the modes that most impact the magnetic ion occur at the lowest energies for 1, at intermediate energies for 2 and at higher energies for 3, in correlation with their ability to retain magnetisation. Therefore, we conclude that SMM performance could be improved by employing more rigid ligands with higher-energy metal-ligand vibrational modes.

Across the periodic table the trans-influence operates, whereby tightly bonded ligands selectively lengthen mutually trans metal-ligand bonds. Conversely, in high oxidation state actinide complexes the inverse-trans-influence operates, where normally cis strongly donating ligands instead reside trans and actually reinforce each other. However, because the inverse-trans-influence is restricted to high-valent actinyls and a few uranium(V/VI) complexes, it has had limited scope in an area with few unifying rules. Here we report tetravalent cerium, uranium and thorium bis(carbene) complexes with trans C=M=C cores where experimental and theoretical data suggest the presence of an inverse-trans-influence. Studies of hypothetical praseodymium(IV) and terbium(IV) analogues suggest the inverse-trans-influence may extend to these ions but it also diminishes significantly as the 4f orbitals are populated. This work suggests that the inverse-trans-influence may occur beyond high oxidation state 5f metals and hence could encompass mid-range oxidation state actinides and lanthanides. Thus, the inverse-trans-influence might be a more general f-block principle.

We report a monometallic dysprosium(iii) single molecule magnet with record energy barriers and unusual spin relaxation behaviour., We report a dysprosium(iii) bis(methanediide) single molecule magnet (SMM) where stabilisation of the highly magnetic states and suppression of mixing of opposite magnetic projections is imposed by a linear arrangement of negatively-charged donor atoms supported by weak neutral donors. Treatment of [Ln(BIPMTMS)(BIPMTMSH)] [Ln = Dy, 1Dy; Y, 1Y; BIPMTMS = {C(PPh2NSiMe3)2}2–; BIPMTMSH = {HC(PPh2NSiMe3)2}–] with benzyl potassium/18-crown-6 ether (18C6) in THF afforded [Ln(BIPMTMS)2][K(18C6)(THF)2] [Ln = Dy, 2Dy; Y, 2Y]. AC magnetic measurements of 2Dy in zero DC field show temperature- and frequency-dependent SMM behaviour. Orbach relaxation dominates at high temperature, but at lower temperatures a second-order Raman process dominates. Complex 2Dy exhibits two thermally activated energy barriers (Ueff) of 721 and 813 K, the largest Ueff values for any monometallic dysprosium(iii) complex. Dilution experiments confirm the molecular origin of this phenomenon. Complex 2Dy has rich magnetic dynamics; field-cooled (FC)/zero-field cooled (ZFC) susceptibility measurements show a clear divergence at 16 K, meaning the magnetic observables are out-of-equilibrium below this temperature, however the maximum in ZFC, which conventionally defines the blocking temperature, TB, is found at 10 K. Magnetic hysteresis is also observed in 10% 2Dy@2Y at these temperatures. Ab initio calculations suggest the lowest three Kramers doublets of the ground 6H15/2 multiplet of 2Dy are essentially pure, well-isolated |±15/2, |±13/2 and |±11/2 states quantised along the C 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 Dy 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 C axis. Thermal relaxation occurs via the 4th and 5th doublets, verified experimentally for the first time, and calculated Ueff values of 742 and 810 K compare very well to experimental magnetism and luminescence data. This work validates a design strategy towards realising high-temperature SMMs and produces unusual spin relaxation behaviour where the magnetic observables are out-of-equilibrium some 6 K above the formal blocking temperature.

Against expectations the covalency in a cerium(iv)–carbon multiple bond interaction is essentially as covalent as the uranium(iv) analogue., We report comparable levels of covalency in cerium– and uranium–carbon multiple bonds in the iso-structural carbene complexes [M(BIPMTMS)(ODipp)2] [M = Ce (1), U (2), Th (3); BIPMTMS = C(PPh2NSiMe3)2; Dipp = C6H3-2,6-iPr2] whereas for M = Th the M 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 C bond interaction is much more ionic. On the basis of single crystal X-ray diffraction, NMR, IR, EPR, and XANES spectroscopies, and SQUID magnetometry complexes 1–3 are confirmed formally as bona fide metal(iv) complexes. In order to avoid the deficiencies of orbital-based theoretical analysis approaches we probed the bonding of 1–3via analysis of RASSCF- and CASSCF-derived densities that explicitly treats the orbital energy near-degeneracy and overlap contributions to covalency. For these complexes similar levels of covalency are found for cerium(iv) and uranium(iv), whereas thorium(iv) is found to be more ionic, and this trend is independently found in all computational methods employed. The computationally determined trends in covalency of these systems of Ce ∼ U > Th are also reproduced in experimental exchange reactions of 1–3 with MCl4 salts where 1 and 2 do not exchange with ThCl4, but 3 does exchange with MCl4 (M = Ce, U) and 1 and 2 react with UCl4 and CeCl4, respectively, to establish equilibria. This study therefore provides complementary theoretical and experimental evidence that contrasts to the accepted description that generally lanthanide–ligand bonding in non-zero oxidation state complexes is overwhelmingly ionic but that of uranium is more covalent.

Treatment of [Li{HC(PPh2NSiMe3)2}]2 with 2 equiv of [MOR] (M = Rb, Cs; OR = 2-ethylhexoxide) afforded the heavy group 1 methanides [Rb{HC(PPh2NSiMe3)2}(THF)2] (1) and [Cs{HC(PPh2NSiMe3)2}(DME)2] (2), which do not exhibit methanide C···M contacts in the solid state. Following a literature procedure, H2C(PPh2)2 was reacted with 2 equiv of AdN3 (Ad = adamantyl) to give H2C(PPh2NAd)2 (3). Reaction of 3 with 1 equiv of ButLi in toluene afforded dimeric [Li{HC(PPh2NAd)2}]2 (4). Treatment of 3 with 1 equiv of [M(Bn)] (M = Na, K; Bn = CH2C6H5) in THF gave the Lewis base adducts [M{HC(PPh2NAd)2}(THF)2] [M = Na (5), K (6)]. The heavy group 1 methanides [Rb{HC(PPh2NAd)2}(THF)2] (7) and [Cs{HC(PPh2NAd)2}(DME)2] (8) were prepared by the reaction of [MOR] (M = Rb, Cs; OR = 2-ethylhexoxide) with 4 or reaction of [Cs(Bn)] with 3. The synthetic utility of these group 1 transfer agents has been demonstrated by the preparation of [La{HC(PPh2NR)2}(I)2(THF)] [R = SiMe3 (9), Ad (10)] from [La(I)3(THF)4], employing a salt metat...

Treatment of H2C(PPh2NMes)2 (Mes = 2,4,6-trimethylphenyl) with 1 equiv of [Na(Bn)] (Bn = CH2C6H5) in THF gave the Lewis base adduct [Na{HC(PPh2NMes)2}(THF)2] (1). The heavy group 1 methanides [Rb{HC(PPh2NMes)2}(DME)2] (2) and [Cs{HC(PPh2NMes)2}]6 (3) were prepared by the reaction of [MOR] (M = Cs, Rb; OR = 2-ethylhexoxide) with [Li{HC(PPh2NMes)2}]. The Lewis base adduct 2 is monomeric, but 3 exists as a novel cyclic 2.9 nm hexamer in the solid state even though it was recrystallized from the strong donor solvent THF. The reaction of H2C(PPh2NDipp)2 (Dipp = 2,6-diisopropylphenyl) with [Na(Bn)] afforded [Na{HC(PPh2NDipp)2}(THF)] (4). The potassium congener [K{HC(PPh2NDipp)2}(THF)2] (5) was prepared by the reaction of the parent methane with KH. In 5, the methanide ligand is bound to potassium through one N center, the methanide center, and an η6-Dipp interaction. However, the THF molecules in 5 are loosely bound, as evidenced by the isolation of dimeric [{K[HC(PPh2NDipp)2](THF)}2] (6) from hexane. In 6, the...

After seminal reports of covalent uranium carbene U˭C complexes in the 1980s by Gilje, the area fell dormant for around 30 years. However, in the past five years, there has been a resurgence of interest in the area. Despite recent advances, the classification of these U˭C complexes as either methanediides, carbenes, or alkylidenes has remained a contentious issue. Herein, we review U˭C complexes reported to date, along with reactivity and computational studies, and conclude that although U˭C complexes sit midway on the continuum between rare-earth methanediides and Schrock-type alkylidenes, they can be justifiably described as carbenes.

Straightforward access to a cerium(IV)-carbene complex was provided by one-electron oxidation of an anionic "ate" cerium(III)-carbene precursor, thereby avoiding decomposition reactions that plague oxidations of neutral cerium(III) compounds. The cerium(IV)-carbene complex is the first lanthanide(IV)-element multiple bond and involves a twofold bonding interaction of two electron pairs between cerium and carbon.