In Situ High-Temperature Raman Spectroscopy of UCl3: A Combined Experimental and Theoretical Study.

Uranium trichloride (UCl3) has received growing interest for its use in uranium-fueled molten salt reactors and in the pyrochemical processing of used fuel. In this paper, we report for the first time the experimentally determined Raman spectra of UCl3, at both ambient condition and in situ high temperatures up to 871 K. The frequencies of five of the Raman-active vibrational modes (vi) of UCl3 exhibit a negative temperature derivative ((∂νi/∂T)P) with increasing temperature. This red-shift behavior is likely due to the elongation of U-Cl bonds. The average isobaric mode Grüneisen parameter (γiP = 0.91 ± 0.02) of UCl3 was determined through use of the coefficient of thermal expansion published in Vogel et al. (2021) and the (∂νi/∂T)P values determined in this study. These results are in general agreement with those calculated here by density functional theory (DFT+U). Finally, a comparison of the ambient band positions of UCl3 to those of isostructural lanthanide (La-Eu) and actinide chlorides (Am-Cf) has been made.

Detection of natural abundance 13C J-couplings at Earth's magnetic field for spin system differentiation of small organic molecules.

Nuclear magnetic resonance (NMR) spectroscopy routinely characterizes the unique spin systems of molecules using a combination of chemical shift and J-coupling interactions for the 1H and 13C nuclei. However, at Earth's magnetic field, chemical shifts are unresolvable and the ability to characterize structure relies solely on the J-couplings. Fortuitously, the J-couplings at Earth's field provides the same spin system information as high field, but only requires detection of the 1H nucleus. We report the first identification of the multiple natural abundance 1H-13C spin systems on organic molecules detected at Earth's magnetic field. The results clearly demonstrate the feasibility of Earth's field NMR to characterize small organic molecules without costly enrichment strategies.

Powering the next industrial revolution: transitioning from nonrenewable energy to solar fuels via CO2 reduction.

Solar energy has been used for decades for the direct production of electricity in various industries and devices; however, harnessing and storing this energy in the form of chemical bonds has emerged as a promising alternative to fossil fuel combustion. The common feedstocks for producing such solar fuels are carbon dioxide and water, yet only the photoconversion of carbon dioxide presents the opportunity to generate liquid fuels capable of integrating into our existing infrastructure, while simultaneously removing atmospheric greenhouse gas pollution. This review presents recent advances in photochemical solar fuel production technology. Although efforts in this field have created an incredible number of methods to convert carbon dioxide into gaseous and liquid fuels, these can generally be classified under one of four categories based on how incident sunlight is utilised: solar concentration for thermoconversion (Category 1), transformation toward electroconversion (Category 2), natural photosynthesis for bioconversion (Category 3), and artificial photosynthesis for direct photoconversion (Category 4). Select examples of developments within each of these categories is presented, showing the state-of-the-art in the use of carbon dioxide as a suitable feedstock for solar fuel production.

Photoluminescence of Visible and NIR-Emitting Lanthanide-Doped Bismuth-Organic Materials.

A bismuth-organic compound containing 2,2':6'2"-terpyridine (terpy) and 2-thiophenecarboxylate (TC), of the general formula (terpy)Bi(κ2 -TC)3 ⋅0.47 H2 O (BiOM-1), has been synthesized under hydrothermal conditions. Addition of a lanthanide nitrate solution to the reaction mixture led to statistical replacement of the bismuth centers, and yielded isomorphous lanthanide containing compounds Bi1-x Lnx OM-1 (Ln=Nd, Sm, Eu, Tb, Dy, Er, and Yb) that showed bismuth and/or ligand sensitized lanthanide-centered emission, and the first example of NIR emission from a lanthanide doped BiOM. The structure was determined by single-crystal X-ray diffraction, and the level and uniformity of lanthanide ion incorporation into the bismuth host was determined by ICP-OES and electron microprobe analysis. For the visible emitters, lifetime data and quantum yields are presented. A high efficiency of sensitization was calculated for the europium analog (50.1 %), showing significant improvement over previously reported europium thiophenecarboxylates. These novel materials may provide strategies to address concerns over the long-term sustainability of the rare earth elements, especially relating to optical devices.

Synthesis of Coordinatively Unsaturated Tetravalent Actinide Complexes with η(5) Coordination of Pyrrole.

The synthesis of new actinide complexes utilizing bridged α-alkyl-pyrrolyl ligands is presented. Lithiation of the ligands followed by treatment with 1 equiv of actinide tetrachloride (uranium or thorium) produces the desired complex in good yield. X-ray diffraction studies reveal unique η(5):η(5) coordination of the pyrrolyl moieties; when the nonsterically demanding methylated ligand is used, rapid addition of the lithiated ligand solution to the metal precursor forms a bis-ligated complex that reveals η(5):η(1) coordination as determined by crystallographic analysis.

Actinide-Catalyzed Intermolecular Addition of Alcohols to Carbodiimides.

The unprecedented actinide-catalyzed addition of alcohols to carbodiimides is presented. This represents a rare example of thorium-catalyzed transformations of an alcoholic substrate and the first example of uranium complexes showing catalytic reactivity with alcohols. Using the uranium and thorium amides U[N(SiMe3)2]3 and [(Me3Si)2N]2An[κ(2)-(N,C)-CH2Si(CH3)2N(SiMe3)] (An = Th or U), alcohol additions to unsaturated carbon-nitrogen bonds are achieved in short reaction times with excellent selectivities and high to excellent yields. Computational studies, supported by experimental thermodynamic data, suggest plausible models of the profile of the reaction which allow the system to overcome the high barrier of scission of the actinide-oxygen bond. Accompanied by experimentally determined kinetic parameters, a plausible mechanism is proposed for the catalytic cycle.

Catalytic insertion of E-H bonds (E = C, N, P, S) into heterocumulenes by amido-actinide complexes.

We report herein the actinide-mediated insertion of E-H bonds (E = C, N, P, S) into various heterocumulenes including carbodiimides, isocyanates, and isothiocyanates. The precatalysts are prepared by a simple, one-pot procedure using readily available starting materials, and challenging insertions are achieved with excellent selectivity in short reaction times. Spectroscopic data are utilised to propose the active catalytic mechanism and derive thermodynamic activation parameters, which are described in this study. The only example of an actinide-mediated C-H bond insertion into a carbon-heteroatom bond is presented within this study.

Organoactinides in the polymerization of ethylene: is TIBA a better cocatalyst than MAO?

The synthesis of two pyridylamidinate bis(N,N'-bis(trimethylsilyl)-2-pyridylamidinate)An(µ-Cl)2Li(TMEDA) (An = U (1), Th (2)) complexes is presented. For complex 1 the solid state X-ray structures were studied and compared to that of complex 2. The organoactinide complexes were studied as pre-catalysts in the polymerization of ethylene when activated by methylalumoxane (MAO). The catalytic activity was improved using a mixture of trityl tetrakispentafluorophenylborate (TTPB) and a small amount of methylalumoxane (MAO) as cocatalysts, and was amazingly improved, providing the greatest activity, using only triisobutyl aluminum (TIBA). We present a combination of ESR, C60 radical trapping, and MALDI-TOF studies describing the formation of the single-site active species, capturing some unique features of the complexes and shedding light on the polymerization mechanism.

Evaluation of donor and steric properties of anionic ligands on high valent transition metals.

Synthetic protocols and characterization data for a variety of chromium(VI) nitrido compounds of the general formula NCr(NPr(i)(2))(2)X are reported, where X = NPr(i)(2) (1), I (2), Cl (3), Br (4), OTf (5), 1-adamantoxide (6), OSiPh(3) (7), O(2)CPh (8), OBu(t)(F6) (9), OPh (10), O-p-(OMe)C(6)H(4) (11), O-p-(SMe)C(6)H(4) (12), O-p-(Bu(t))C(6)H(4) (13), O-p-(F)C(6)H(4) (14), O-p-(Cl)C(6)H(4) (15), O-p-(CF(3))C(6)H(4) (16), OC(6)F(5) (17), κ(O)-N-oxy-phthalimide (18), SPh (19), OCH(2)Ph (20), NO(3) (21), pyrrolyl (22), 3-C(6)F(5)-pyrrolyl (23), 3-[3,5-(CF(3))(2)C(6)H(3)]pyrrolyl (24), indolyl (25), carbazolyl (26), N(Me)Ph (27), κ(N)-NCO (28), κ(N)-NCS (29), CN (30), NMe(2) (31), F (33). Several different techniques were employed in the syntheses, including nitrogen-atom transfer for the formation of 1. A cationic chromium complex [NCr(NPr(i)(2))(2)(DMAP)]BF(4) (32) was used as an intermediate for the production of 33, which was produced by tin-catalyzed degredation of the salt. Using spin saturation transfer or line shape analysis, the free energy barriers for diisopropylamido rotation were studied. It is proposed that the estimated enthalpic barriers, Ligand Donor Parameters (LDPs), for amido rotation can be used to parametrize the donor abilities of this diverse set of anionic ligands toward transition metal centers in low d-electron counts. The new LDPs do not correlate well to the pK(a) value of X. Conversely, the LDP values of phenoxide ligands do correlate with Hammett parameters for the para-substituents. Literature data for (13)C NMR chemical shifts for a tungsten-based system with various X ligands plotted versus LDP provided a linear fit. In addition, the angular overlap model derived e(σ) + e(π) values for chromium(III) ammine complexes correlate with LDP values. Also discussed is the correlation with XTiCp*(2) spectroscopic data. X-ray diffraction has been used used to characterize 31 of the compounds. From the X-ray diffraction data, steric parameters for the ligands using the Percent Buried Volume and Solid Angle techniques were found.

Chlorido(4,4',4''-tri-tert-butyl-2,2':6',2''-terpyridine)-platinum(II) tetra-fluorido-borate.

In the title compound, [PtCl(C(27)H(35)N(3))]BF(4), the Pt(II) atom is in a pseudo-square-planar coordination, which is typical of Pt-terpyridine complexes. The Pt-Cl bond distance is 2.2998 (7) Å. The Pt-N distance of the N atom on the central pyridine is 1.931 (2) Å, while the peripheral N atoms have Pt-N distances of 2.018 (2) and 2.022 (2) Å. The cations pack as dimers in a head-to-tail orientation with an inter-molecular Pt⋯Pt distance of 3.5214 (2) Šand Pt⋯N distances of 3.527 (2), 3.873 (2) and 4.532 (2) Å. In the crystal, cations and anions are linked by weak C-H⋯F hydrogen-bonding inter-actions.

Chlorido(4,4',4''-tri-tert-butyl-2,2':6',2''-terpyridine)-platinum(II) chloride toluene monosolvate.

In the title compound, [PtCl(C(27)H(35)N(3))]Cl·C(7)H(8), the Pt(II) atom is coordinated in a pseudo-square-planar fashion by the N atoms of a 4,4',4''-tri-tert-butyl-2,2':6',2''-terpyridine (tbtrpy) ligand and a Cl atom. The Pt-N distance of the N atom on the central pyridine is 1.941 (4) Å, while the peripheral N atoms have Pt-N distances of 2.015 (4) and 2.013 (4) Å. The Pt-Cl bond distance is 2.3070 (10) Å. The cations pack as dimers in a head-to-tail orientation with an inter-molecular Pt⋯Pt distance of 3.2774 (3) Šand Pt⋯N distances of 3.599 (4), 3.791 (4) and 4.115 (4) Å. The solvent mol-ecule is disordered and occupies two positions with a ratio of 0.553 (6):0.447 (6).