Arene-, Chlorido-, and Imido-Uranium Bis- and Tris(boryloxide) Complexes.

We introduce the boryloxide ligand {(HCNDipp)2BO}- (NBODipp, Dipp = 2,6-di-isopropylphenyl) to actinide chemistry. Protonolysis of [U{N(SiMe3)2}3] with 3 equiv of NBODippH produced the uranium(III) tris(boryloxide) complex [U(NBODipp)3] (1). In contrast, treatment of UCl4 with 3 equiv of NBODippK in THF at room temperature or reflux conditions produced only [U(NBODipp)2(Cl)2(THF)2] (2) with 1 equiv of NBODippK remaining unreacted. However, refluxing the mixture of 2 and unreacted NBODippK in toluene instead of THF afforded the target complex [U(NBODipp)3(Cl)(THF)] (3). Two-electron oxidation of 1 with AdN3 (Ad = 1-adamantyl) afforded the uranium(V)-imido complex [U(NBODipp)3(NAd)] (4). The solid-state structure of 1 reveals a uranium-arene bonding motif, and structural, spectroscopic, and DFT calculations all suggest modest uranium-arene δ-back-bonding with approximately equal donation into the arene π4 and π5 δ-symmetry π* molecular orbitals. Complex 4 exhibits a short uranium(V)-imido distance, and computational modeling enabled its electronic structure to be compared to related uranium-imido and uranium-oxo complexes, revealing a substantial 5f-orbital crystal field splitting and extensive mixing of 5f |ml,ms⟩ states and mj projections. Complexes 1-4 have been variously characterized by single-crystal X-ray diffraction, 1H NMR, IR, UV/vis/NIR, and EPR spectroscopies, SQUID magnetometry, elemental analysis, and CONDON, F-shell, DFT, NLMO, and QTAIM crystal field and quantum chemical calculations.

Thorium(IV)-antimony complexes exhibiting single, double, and triple polar covalent metal-metal bonds.

There is continued burgeoning interest in metal-metal multiple bonding to further our understanding of chemical bonding across the periodic table. However, although polar covalent metal-metal multiple bonding is well known for the d and p blocks, it is relatively underdeveloped for actinides. Homometallic examples are found in spectroscopic or fullerene-confined species, and heterometallic variants exhibiting a polar covalent σ bond supplemented by up to two dative π bonds are more prevalent. Hence, securing polar covalent actinide double and triple metal-metal bonds under normal experimental conditions has been a fundamental target. Here we exploit the protonolysis and dehydrocoupling chemistry of the parent dihydrogen-antimonide anion, to report one-, two- and three-fold thorium-antimony bonds, thus introducing polar covalent actinide-metal multiple bonding under normal experimental conditions between some of the heaviest ions in the periodic table with little or no bulky-substituent protection at the antimony centre. This provides fundamental insights into heavy element multiple bonding, in particular the tension between orbital-energy-driven and overlap-driven covalency for the actinides in a relativistic regime.

Carbene Complexes of Plutonium: Structure, Bonding, and Divergent Reactivity to Lanthanide Analogs.

Organoplutonium chemistry was established in 1965, yet structurally authenticated plutonium-carbon bonds remain rare being limited to π-bonded carbocycle and σ-bonded isonitrile and hydrocarbyl derivatives. Thus, plutonium-carbenes, including alkylidenes and N-heterocyclic carbenes (NHCs), are unknown. Here, we report the preparation and characterization of the diphosphoniomethanide-plutonium complex [Pu(BIPMTMSH)(I)(µ-I)]2 (1Pu, BIPMTMSH = (Me3SiNPPh2)2CH) and the diphosphonioalkylidene-plutonium complexes [Pu(BIPMTMS)(I)(DME)] (2Pu, BIPMTMS = (Me3SiNPPh2)2C) and [Pu(BIPMTMS)(I)(IMe4)2] (3Pu, IMe4 = C(NMeCMe)2), thus disclosing non-actinyl transneptunium multiple bonds and transneptunium NHC complexes. These Pu-C double and dative bonds, along with cerium, praseodymium, samarium, uranium, and neptunium congeners, enable lanthanide-actinide and actinide-actinide comparisons between metals with similar ionic radii and isoelectronic 4f5 vs 5f5 electron-counts within conserved ligand fields over 12 complexes. Quantum chemical calculations reveal that the orbital-energy and spatial-overlap terms increase from uranium to neptunium; however, on moving to plutonium the orbital-energy matching improves but the spatial overlap decreases. The bonding picture that emerges is more complex than the traditional picture of the bonding of lanthanides being ionic and early actinides being more covalent but becoming more ionic left to right. Multiconfigurational calculations on 2M and 3M (M = Pu, Sm) account for the considerably more complex UV/vis/NIR spectra for 5f5 2Pu and 3Pu compared to 4f5 2Sm and 3Sm. Supporting the presence of Pu═C double bonds in 2Pu and 3Pu, 2Pu exhibits metallo-Wittig bond metathesis involving the highest atomic number element to date, reacting with benzaldehyde to produce the alkene PhC(H)═C(PPh2NSiMe3)2 (4) and "PuOI". In contrast, 2Ce and 2Pr do not react with benzaldehyde to produce 4.

Comparison of group 4 and thorium M(IV) substituted cyclopentadienyl silanide complexes.

We report the synthesis and characterisation of a series of M(IV) substituted cyclopentadienyl hypersilanide complexes of the general formula [M(CpR)2{Si(SiMe3)3}(X)] (M = Hf, Th; CpR = Cp', {C5H4(SiMe3)} or Cp'', {C5H3(SiMe3)2-1,3}; X = Cl, C3H5). The separate salt metathesis reactions of [M(CpR)2(Cl)2] (M = Zr or Hf, CpR = Cp'; M = Hf or Th, CpR = Cp'') with equimolar K{Si(SiMe3)3} gave the respective mono-silanide complexes [M(Cp')2{Si(SiMe3)3}(Cl)] (M = Zr, 1; Hf, 2), [Hf(Cp'')(Cp'){Si(SiMe3)3}(Cl)] (3) and [Th(Cp'')2{Si(SiMe3)3}(Cl)] (4), with only a trace amount of 3 presumably formed via silatropic and sigmatropic shifts; the synthesis of 1 from [Zr(Cp')2(Cl)2] and Li{Si(SiMe3)3} has been reported previously. The salt elimination reaction of 2 with one equivalent of allylmagnesium chloride gave [Hf(Cp')2{Si(SiMe3)3}(η3-C3H5)] (5), whilst the corresponding reaction of 2 with equimolar benzyl potassium yielded [Hf(Cp')2(CH2Ph)2] (6) together with a mixture of other products, with elimination of both KCl and K{Si(SiMe3)3}. Attempts to prepare isolated [M(CpR)2{Si(SiMe3)3}]+ cations from 4 or 5 by standard abstraction methodologies were unsuccessful. The reduction of 4 with KC8 gave the known Th(III) complex, [Th(Cp'')3]. Complexes 2-6 were characterised by single crystal XRD, whilst 2, 4 and 5 were additionally characterised by 1H, 13C{1H} and 29Si{1H} NMR spectroscopy, ATR-IR spectroscopy and elemental analysis. In order to probe differences in M(IV)-Si bonds for d- and f-block metals we studied the electronic structures of 1-5 by density functional theory calculations, showing M-Si bonds of similar covalency for Zr(IV) and Hf(IV), and less covalent M-Si bonds for Th(IV).

Electronic structure comparisons of isostructural early d- and f-block metal(iii) bis(cyclopentadienyl) silanide complexes.

We report the synthesis of the U(iii) bis(cyclopentadienyl) hypersilanide complex [U(Cp'')2{Si(SiMe3)3}] (Cp'' = {C5H3(SiMe3)2-1,3}), together with isostructural lanthanide and group 4 M(iii) homologues, in order to meaningfully compare metal-silicon bonding between early d- and f-block metals. All complexes were characterised by a combination of NMR, EPR, UV-vis-NIR and ATR-IR spectroscopies, single crystal X-ray diffraction, SQUID magnetometry, elemental analysis and ab initio calculations. We find that for the [M(Cp'')2{Si(SiMe3)3}] (M = Ti, Zr, La, Ce, Nd, U) series the unique anisotropy axis is conserved tangential to ; this is governed by the hypersilanide ligand for the d-block complexes to give easy plane anisotropy, whereas the easy axis is fixed by the two Cp'' ligands in f-block congeners. This divergence is attributed to hypersilanide acting as a strong σ-donor and weak π-acceptor with the d-block metals, whilst f-block metals show predominantly electrostatic bonding with weaker π-components. We make qualitative comparisons on the strength of covalency to derive the ordering Zr > Ti ≫ U > Nd ≈ Ce ≈ La in these complexes, using a combination of analytical techniques. The greater covalency of 5f3 U(iii) vs. 4f3 Nd(iii) is found by comparison of their EPR and electronic absorption spectra and magnetic measurements, with calculations indicating that uranium 5f orbitals have weak π-bonding interactions with both the silanide and Cp'' ligands, in addition to weak δ-antibonding with Cp''.

Synthesis and Characterization of Yttrium Methanediide Silanide Complexes.

The salt metathesis reactions of the yttrium methanediide iodide complex [Y(BIPM)(I)(THF)2] (BIPM = {C(PPh2NSiMe3)2}) with the group 1 silanide ligand-transfer reagents MSiR3 (M = Na, R3 = tBu2Me or tBu3; M = K, R3 = (SiMe3)3) gave the yttrium methanediide silanide complexes [Y(BIPM)(SitBu2Me)(THF)] (1), [Y(BIPM)(SitBu3)(THF)] (2), and [Y(BIPM){Si(SiMe3)3}(THF)] (3). Complexes 1-3 provide rare examples of structurally authenticated rare earth metal-silicon bonds and were characterized by single-crystal X-ray diffraction, multinuclear NMR and ATR-IR spectroscopies, and elemental analysis. Density functional theory calculations were performed on 1-3 to probe their electronic structures further, revealing predominantly ionic Y-Si bonding. The computed Y-Si bonds show lower covalency than Y═C bonds, which are in turn best represented by Y+-C- dipolar forms due to the strong σ-donor properties of the silanide ligands investigated; these observations are in accord with experimentally obtained 13C{1H} and 29Si{1H} NMR data for 1-3 and related Y(III) BIPM alkyl complexes in the literature. Preliminary reactivity studies were performed, with complex 1 treated separately with benzophenone, azobenzene, and N,N'-dicyclohexyl-carbodiimide. 29Si{1H} and 31P{1H} NMR spectra of these reaction mixtures indicated that 1,2-migratory insertion of the unsaturated substrate into the Y-Si bond is favored, while for the latter substrate, a [2 + 2]-cycloaddition reaction also occurs at the Y═C bond to afford [Y{C(PPh2NSiMe3)2[C(NCy)2]-κ4C,N,N',N'}{C(NCy)2(SitBu2Me)-κ2N,N'}] (4); these reactivity profiles complement and contrast with those of Y(III) BIPM alkyl complexes.

Actinide Pnictinidene Chemistry: A Terminal Thorium Parent-Arsinidene Complex Stabilised by a Super-Bulky Triamidoamine Ligand.

We report the direct synthesis of the terminal pnictidenes [An(TrenTCHS )(PnH)][M(2,2,2-cryptand)] (TrenTCHS ={N(CH2 CH2 NSiCy3 )3 }3- ; An/Pn/M=Th/P/Na 5, Th/As/K 6, U/P/Na 7, U/As/K 8) and their conversion to the pnictides [An(TrenTCHS )(PnH2 )] (An/Pn=Th/P 9, Th/As 10, U/P 11, U/As 12). Use of the super-bulky TrenTCHS ligand was essential to accessing complete families, and 6 is an unprecedented example of a terminal thorium-arsinidene complex and only the second structurally authenticated parent terminal arsinidene complex of any metal. Comparison of the terminal Th=AsH unit of 6 to the bridging ThAs(H)K linkage in structurally analogous [Th(TrenTIPS ){µ-As(H)K(15-crown-5)}] (TrenTIPS ={N(CH2 CH2 NSiPri 3 )3 }3- ) reveals a stronger Th-As bond in the former compared to the latter, and a large response overall to the nature of the Th=AsH bonding upon removal of the electrostatically-bound K-ion; the σ-bond changes little but the π-bond is significantly perturbed.

Mesoionic Carbene Complexes of Uranium(IV) and Thorium(IV).

We report the synthesis and characterization of uranium(IV) and thorium(IV) mesoionic carbene complexes [An{N(SiMe3)2}2(CH2SiMe2NSiMe3){MIC}] (An = U, 4U and Th, 4Th; MIC = {CN(Me)C(Me)N(Me)CH}), which represent rare examples of actinide mesoionic carbene linkages and the first example of a thorium mesoionic carbene complex. Complexes 4U and 4Th were prepared via a C-H activation intramolecular cyclometallation reaction of actinide halides, with concomitant formal 1,4-proton migration of an N-heterocyclic olefin (NHO). Quantum chemical calculations suggest that the An-carbene bond comprises only a σ-component, in contrast to the uranium(III) analogue [U{N(SiMe3)2}3(MIC)] (1) where computational studies suggested that the 5f3 uranium(III) ion engages in a weak one-electron π-backbond to the MIC. This highlights the varying nature of actinide-MIC bonding as a function of actinide oxidation state. In solution, 4Th exists in equilibrium with the Th(IV) metallacycle [Th{N(SiMe3)2}2(CH2SiMe2NSiMe3)] (6Th) and free NHO (3). The thermodynamic parameters of this equilibrium were probed using variable-temperature NMR spectroscopy yielding an entropically favored but enthalpically endothermic process with an overall reaction free energy of ΔG 298.15K = 0.89 kcal mol-1. Energy decomposition analysis (EDA-NOCV) of the actinide-carbon bonds in 4U and 4Th reveals that the former is enthalpically stronger and more covalent than the latter, which accounts for the respective stabilities of these two complexes.

Uranium-nitride chemistry: uranium-uranium electronic communication mediated by nitride bridges.

Treatment of [UIV(N3)(TrenTIPS)] (1, TrenTIPS = {N(CH2CH2NSiPri3)3}3-) with excess Li resulted in the isolation of [{UIV(µ-NLi2)(TrenTIPS)}2] (2), which exhibits a diuranium(IV) 'diamond-core' dinitride motif. Over-reduction of 1 produces [UIII(TrenTIPS)] (3), and together with known [{UV(µ-NLi)(TrenTIPS)}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 [{UIV(TrenTIPS)}2(µ-NH)(µ-NLi2)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 U2N2.

Carbene Complexes of Neptunium.

Since the advent of organotransuranium chemistry six decades ago, structurally verified complexes remain restricted to π-bonded carbocycle and σ-bonded hydrocarbyl derivatives. Thus, transuranium-carbon multiple or dative bonds are yet to be reported. Here, utilizing diphosphoniomethanide precursors we report the synthesis and characterization of transuranium-carbene derivatives, namely, diphosphonio-alkylidene- and N-heterocyclic carbene-neptunium(III) complexes that exhibit polarized-covalent σ2π2 multiple and dative σ2 single transuranium-carbon bond interactions, respectively. The reaction of [NpIIII3(THF)4] with [Rb(BIPMTMSH)] (BIPMTMSH = {HC(PPh2NSiMe3)2}1-) affords [(BIPMTMSH)NpIII(I)2(THF)] (3Np) in situ, and subsequent treatment with the N-heterocyclic carbene {C(NMeCMe)2} (IMe4) allows isolation of [(BIPMTMSH)NpIII(I)2(IMe4)] (4Np). Separate treatment of in situ prepared 3Np with benzyl potassium in 1,2-dimethoxyethane (DME) affords [(BIPMTMS)NpIII(I)(DME)] (5Np, BIPMTMS = {C(PPh2NSiMe3)2}2-). Analogously, addition of benzyl potassium and IMe4 to 4Np gives [(BIPMTMS)NpIII(I)(IMe4)2] (6Np). The synthesis of 3Np-6Np was facilitated by adopting a scaled-down prechoreographed approach using cerium synthetic surrogates. The thorium(III) and uranium(III) analogues of these neptunium(III) complexes are currently unavailable, meaning that the synthesis of 4Np-6Np provides an example of experimental grounding of 5f- vs 5f- and 5f- vs 4f-element bonding and reactivity comparisons being led by nonaqueous transuranium chemistry rather than thorium and uranium congeners. Computational analysis suggests that these NpIII═C bonds are more covalent than UIII═C, CeIII═C, and PmIII═C congeners but comparable to analogous UIV═C bonds in terms of bond orders and total metal contributions to the M═C bonds. A preliminary assessment of NpIII═C reactivity has introduced multiple bond metathesis to transuranium chemistry, extending the range of known metallo-Wittig reactions to encompass actinide oxidation states III-VI.

A Series of Rare-Earth Mesoionic Carbene Complexes.

We report the synthesis and characterisation of a series of rare-earth mesoionic carbene complexes, [RE{N(SiMe3 )2 }3 {CN(Me)C(Me)N(Me)CH}] (3RE, RE=Sc, Ce, Pr, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu), greatly expanding the limited library of f-block mesoionic carbene complexes. These complexes were prepared by treatment of the parent RE-triamides with an N-heterocyclic olefin (NHO), where an NHO backbone proton undergoes a formal 1,4-proton migration to the NHO-methylene group. For all RE(III) metals, as expected, quantum chemical calculations suggest only a σ-component to the metal-carbene bonding, in contrast to a previously reported uranium(III) congener where the 5f3 metal engages in a weak π-back-bond to the MIC. All complexes were characterised by static variable-temperature magnetic measurements, and dynamic magnetic measurements reveal that 3Dy and 3Er are field-induced single-molecule magnets (SMMs), with Ueff energy barriers of 35 and 128 K, respectively. Complex 3Dy is, as expected, a poorly performing SMM, but conversely 3Er performs unexpectedly well.

A terminal neptunium(V)-mono(oxo) complex.

Neptunium was the first actinide element to be artificially synthesized, yet, compared with its more famous neighbours uranium and plutonium, is less conspicuously studied. Most neptunium chemistry involves the neptunyl di(oxo)-motif, and transuranic compounds with one metal-ligand multiple bond are rare, being found only in extended-structure oxide, fluoride or oxyhalide materials. These combinations stabilize the required high oxidation states, which are otherwise challenging to realize for transuranic ions. Here we report the synthesis, isolation and characterization of a stable molecular neptunium(V)-mono(oxo) triamidoamine complex. We describe a strong Np≡O triple bond with dominant 5f-orbital contributions and σu > πu energy ordering, akin to terminal uranium-nitrides and di(oxo)-actinyls, but not the uranium-mono(oxo) triple bonds or other actinide multiple bonds reported so far. This work demonstrates that molecular high-oxidation-state transuranic complexes with a single metal-ligand bond can be stabilized and studied in isolation.

Evidence for ligand- and solvent-induced disproportionation of uranium(IV).

Disproportionation, where a chemical element converts its oxidation state to two different ones, one higher and one lower, underpins the fundamental chemistry of metal ions. The overwhelming majority of uranium disproportionations involve uranium(III) and (V), with a singular example of uranium(IV) to uranium(V/III) disproportionation known, involving a nitride to imido/triflate transformation. Here, we report a conceptually opposite disproportionation of uranium(IV)-imido complexes to uranium(V)-nitride/uranium(III)-amide mixtures. This is facilitated by benzene, but not toluene, since benzene engages in a redox reaction with the uranium(III)-amide product to give uranium(IV)-amide and reduced arene. These disproportionations occur with potassium, rubidium, and cesium counter cations, but not lithium or sodium, reflecting the stability of the corresponding alkali metal-arene by-products. This reveals an exceptional level of ligand- and solvent-control over a key thermodynamic property of uranium, and is complementary to isolobal uranium(V)-oxo disproportionations, suggesting a potentially wider prevalence possibly with broad implications for the chemistry of uranium.

A crystalline tri-thorium cluster with σ-aromatic metal-metal bonding.

Metal-metal bonding is a widely studied area of chemistry1-3, and has become a mature field spanning numerous d transition metal and main group complexes4-7. By contrast, actinide-actinide bonding, which is predicted to be weak8, is currently restricted to spectroscopically detected gas-phase U2 and Th2 (refs. 9,10), U2H2 and U2H4 in frozen matrices at 6-7 K (refs. 11,12), or fullerene-encapsulated U2 (ref. 13). Furthermore, attempts to prepare thorium-thorium bonds in frozen matrices have produced only ThHn (n = 1-4)14. Thus, there are no isolable actinide-actinide bonds under normal conditions. Computational investigations have explored the probable nature of actinide-actinide bonding15, concentrating on localized σ-, π-, and δ-bonding models paralleling d transition metal analogues, but predictions in relativistic regimes are challenging and have remained experimentally unverified. Here, we report thorium-thorium bonding in a crystalline cluster, prepared and isolated under normal experimental conditions. The cluster exhibits a diamagnetic, closed-shell singlet ground state with a valence-delocalized three-centre-two-electron σ-aromatic bond16,17 that is counter to the focus of previous theoretical predictions. The experimental discovery of actinide σ-aromatic bonding adds to main group and d transition metal analogues, extending delocalized σ-aromatic bonding to the heaviest elements in the periodic table and to principal quantum number six, and constitutes a new approach to elaborate actinide-actinide bonding.

29Si NMR Spectroscopy as a Probe of s- and f-Block Metal(II)-Silanide Bond Covalency.

We report the use of 29Si NMR spectroscopy and DFT calculations combined to benchmark the covalency in the chemical bonding of s- and f-block metal-silicon bonds. The complexes [M(SitBu3)2(THF)2(THF)x] (1-M: M = Mg, Ca, Yb, x = 0; M = Sm, Eu, x = 1) and [M(SitBu2Me)2(THF)2(THF)x] (2-M: M = Mg, x = 0; M = Ca, Sm, Eu, Yb, x = 1) have been synthesized and characterized. DFT calculations and 29Si NMR spectroscopic analyses of 1-M and 2-M (M = Mg, Ca, Yb, No, the last in silico due to experimental unavailability) together with known {Si(SiMe3)3}--, {Si(SiMe2H)3}--, and {SiPh3}--substituted analogues provide 20 representative examples spanning five silanide ligands and four divalent metals, revealing that the metal-bound 29Si NMR isotropic chemical shifts, δSi, span a wide (∼225 ppm) range when the metal is kept constant, and direct, linear correlations are found between δSi and computed delocalization indices and quantum chemical topology interatomic exchange-correlation energies that are measures of bond covalency. The calculations reveal dominant s- and d-orbital character in the bonding of these silanide complexes, with no significant f-orbital contributions. The δSi is determined, relatively, by paramagnetic shielding for a given metal when the silanide is varied but by the spin-orbit shielding term when the metal is varied for a given ligand. The calculations suggest a covalency ordering of No(II) > Yb(II) > Ca(II) ≈ Mg(II), challenging the traditional view of late actinide chemical bonding being equivalent to that of the late lanthanides.

Correlating axial and equatorial ligand field effects to the single-molecule magnet performances of a family of dysprosium bis-methanediide complexes.

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 (U eff) of 1069(129)/1160(21), 1015(32), 1109(70), and 757(39) K, respectively, thus 2Dy-4Dy join a privileged group of SMMs with U eff 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[double bond, length as m-dash]Dy[double bond, length as m-dash]C units with short average Dy[double bond, length as m-dash]C distances, and the latter have more bent C[double bond, length as m-dash]Dy[double bond, length as m-dash]C units with longer average Dy[double bond, length as m-dash]C bonds. Both U eff 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 U eff barrier and axial linearity in structurally comparable systems.

Fragmentation, catenation, and direct functionalisation of white phosphorus by a uranium(IV)-silyl-phosphino-carbene complex.

Room temperature reaction of the uranium(iv)-carbene [U{C(SiMe3)(PPh2)}(BIPMTMS)(µ-Cl)Li(TMEDA)(µ-TMEDA)0.5]2 (1, BIPMTMS = C(PPh2NSiMe3)2) with white phosphorus (P4) produces the organo-P5 compound [P5{C(SiMe3)(PPh2)}2][Li(TMEDA)2] (2) and the uranium(iv)-methanediide [U{BIPMTMS}{Cl}{µ-Cl}2{Li(TMEDA)}] (3). This is an unprecedented example of cooperative metal-carbene P4 activation/insertion into a metal-carbon double bond and also an actinide complex reacting with P4 to directly form an organophosphorus species. Conducting the reaction at low temperature permits the isolation of the diuranium(iv) complex [{U(BIPMTMS)([µ-η2:η2-P2]C[SiMe3][PPh2])}2] (4), which then converts to 2 and 3. Thus, surprisingly, in contrast to all other actinide P4 reactivity, although this reaction produces catenation overall it proceeds via P4 cleavage to functionalised P2 units. Hence, this work establishes a proof of concept synthetic cycle for direct fragmentation, catenation, and functionalisation of P4.

Dipnictogen f-Element Chemistry: A Diphosphorus Uranium Complex.

The first isolation and structural characterization of an f-element dinitrogen complex was reported in 1988, but an f-element complex with the first heavier group 15 homologue diphosphorus has to date remained unknown. Here, we report the synthesis of a side-on bound diphosphorus complex of uranium(IV) using a 7λ3-(dimethylamino)phosphadibenzonorbornadiene-mediated P atom transfer approach. Experimental and computational characterization reveals that the diphosphorus ligand is activated to its dianionic (P2)2- form and that in-plane U-P π-bonding dominates the bonding of the U(µ-η2:η2-P2)U unit, which is supplemented by a weak U-P interaction of δ symmetry. A preliminary reactivity study demonstrates conversion of this diphosphorus complex to unprecedented uranium cyclo-P3 complexes, suggesting in situ generation of transient, reactive phosphido species.