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We describe the syntheses of a series of sodium aminodiboranate salts, Na(H

Qualitative differences in the reactivity of trivalent lanthanide and actinide complexes have long been attributed to differences in covalent metal-ligand bonding, but there are few examples where thermodynamic aspects of this relationship have been quantified, especially with U

Tandem catalysts that perform two different organic transformations in a single pot are highly desirable because they enable rapid and efficient assembly of simple organic building blocks into more complex molecules. Many examples of tandem catalysis rely on metal-catalyzed reactions involving one or more metal complexes. Remarkably, despite surging interest in the development of chemically reactive (i. e., non-innocent) ligands, there are few examples of metal complexes that leverage ligand-centered reactivity to perform catalytic reactions in tandem with separate catalytic reactions at the metal. Here we report how multifunctional Pd complexes with triaminoborane-derived diphosphorus ligands, called TBDPhos, appear to facilitate borenium-catalyzed cycloaddition reactions at the ligand, and Pd-catalyzed Stille and Suzuki cross-coupling reactions at the metal. Both transformations can be accessed in one pot to afford rare examples of tandem catalysis using separate metal and ligand catalysis sites in a single complex.

Here we report the synthesis, characterization, and hydrolytic stability of water-soluble Pt(ii) complexes containing a triaminoborane-bridged diphosphoramidite ligand that can be fluorinated using simple fluoride salts.

Low-valent uranium coordination chemistry continues to rely heavily on access to trivalent starting materials, but these reagents are typically prepared from uranium turnings, which are becoming increasingly difficult to acquire. Here we report convenient syntheses of UI3(THF)4 (THF = tetrahydrofuran) and UBr3(THF)4 from UCl4, a more accessible uranium starting material that can be prepared from commercially available uranium oxides. UCl3(THF)2 (1), UBr3(THF)4 (2), and UI3(THF)4 (3) were prepared by single-pot reductions from UCl4 using KH and KC8 and converted to 2 or 3 by halide exchange with the corresponding Me3SiX (where X = Br or I). Reduction of UI4(Et2O)2 (4; Et2O = diethyl ether) and UI4(1,4-dioxane)2 (5) was also shown to cleanly yield 3. Complex 1 was also synthesized separately by the addition of anhydrous HCl to U(BH4)3(THF)2, which was prepared by thermal reduction of U(BH4)4. All three trivalent uranium halide complexes were isolated in high crystalline yields (typically 85-99%) and their formulations were confirmed by single-crystal X-ray diffraction, elemental analysis, and 1H NMR and IR spectroscopy. Elemental analysis conducted on triplicate samples of 1-3 exposed to vacuum for different time intervals revealed significant THF loss for all three complexes in as little as 15 min. Overall, these results offer expedient entry into low-valent uranium chemistry for researchers lacking access to uranium turnings.

Phosphinodiboranates (H3BPR2BH3−) are a class of borohydrides that have merited a reputation as weakly coordinating anions, which is attributed in part to the dearth of coordination complexes known with transition metals, lanthanides, and actinides. We recently reported how K(H3BPtBu2BH3) exhibits sluggish salt elimination reactivity with f-metal halides in organic solvents such as Et2O and THF. Here we report how this reactivity appears to be further attenuated in solution when the tBu groups attached to phosphorus are exchanged for R = Ph or H, and we describe how mechanochemistry was used to overcome limited solution reactivity with K(H3BPPh2BH3). Grinding three equivalents of K(H3BPPh2BH3) with UI3(THF)4 or LnI3 (Ln = Ce, Pr, Nd) allowed homoleptic complexes with the empirical formulas U(H3BPPh2BH3)3 (1), Ce(H3BPPh2BH3)3 (2), Pr(H3BPPh2BH3)3 (3), and Nd(H3BPPh2BH3)3 (4) to be prepared and subsequently crystallized in good yields (50–80%). Single-crystal XRD studies revealed that all four complexes exist as dimers or coordination polymers in the solid-state, whereas 1H and 11B NMR spectra showed that they exist as a mixture of monomers and dimers in solution. Treating 4 with THF breaks up the dimer to yield the monomeric complex Nd(H3BPPh2BH3)3(THF)3 (4-THF). XRD studies revealed that 4-THF has one chelating and two dangling H3BPPh2BH3− ligands bound to the metal to accommodate binding of THF. In contrast to the results with K(H3BPPh2BH3), attempting the same mechanochemical reactions with Na(H3BPH2BH3) containing the simplest phosphinodiboranate were unsuccessful; only the partial metathesis product U(H3BPH2BH3)I2(THF)3 (5) was isolated in poor yields. Despite these limitations, our results offer new examples showing how mechanochemistry can be used to rapidly synthesize molecular coordination complexes that are otherwise difficult to prepare using more traditional solution methods.

Here we show that the praseodymium

A number of technologies would benefit from developing inorganic compounds and materials with specific electronic and magnetic exchange properties. Unfortunately, designing compounds with these properties is difficult because metal⋅⋅⋅metal coupling schemes are hard to predict and control. Fully characterizing communication between metals in existing compounds that exhibit interesting properties could provide valuable insight and advance those predictive capabilities. One such class of molecules are the series of Lindqvist iron-functionalized and hexavanadium polyoxovanadate-alkoxide clusters, which we characterized here using V K-edge X-ray absorption spectroscopy. Substantial changes in the pre-edge peak intensities were observed that tracked with the V 3d-electron count. The data also suggested substantial delocalization between the vanadium cations. Meanwhile, the FeIII cations were electronically isolated from the polyoxovanadate core.

Metal–ligand cooperativity (MLC) relies on chemically reactive ligands to assist metals with small-molecule binding and activation, and it has facilitated unprecedented examples of catalysis with m...

Triaminoborane-bridged diphosphorus ligands called TBDPhos can undergo cooperative ligand-centered reactions at the 1,8,10,9-triazaboradecalin (TBD) backbone while bound to metals, but the factors ...

Here we report how reactions at a chemically reactive diphosphine shift the long-lived luminescent colour of a crystalline three-coordinate Cu(i) complex from green to blue. The results demonstrate how vapochromism and single-crystal-to-single-crystal transformations can be achieved using ligand-centered reactions.

Metal-ligand cooperativity (MLC), a phenomenon that leverages reactive ligands to promote synergistic reactions with metals, has proven to be a powerful approach to achieving new and unprecedented chemical transformations with metal complexes. While many examples of MLC are known with a wide range of substrates, experimentally quantifying how ligand modifications affect MLC binding strength remains a challenge. Here we describe how cyclic voltammetry (CV) was used to quantify differences in MLC binding strength in a series of square-pyramidal Ru complexes. This method relies on using multifunctional ligands (those capable of both MLC and ligand-centered redox activity) as electrochemical reporters of MLC binding strength. The synthesis and characterization of Ru complexes with three different redox-active tetradentate ligands and two different ancillary phosphines (PPh

The continued development of redox-active ligands requires an understanding as to how ligand modifications and related factors affect the locus of redox activity and spin density in metal complexes...

We report the small-scale synthesis, isolated yield, single-crystal X-ray structure, 1H NMR solution spectroscopy /solid-state UV/Vis-nIR spectroscopy, and density functional theory (DFT)/ab initio wave function theory calculations on an Am3+ organometallic complex, [Am(C5Me4H)3] (1). This constitutes the first quantitative data on Am−C bonding in a molecular species.

Constraining σ3-P compounds in nontrigonal, entatic geometries has proven to be an effective strategy for promoting biphilic oxidative addition reactions more typical of transition metals. Although qualitative descriptions of the impact of structure and symmetry on σ3-P complexes have been proposed, electronic structure variations responsible for biphilic reactivity have yet to be elucidated experimentally. Reported here are P K-edge XANES data and complementary TDDFT calculations for a series of structurally modified P(N)3 complexes that both validate and quantify electronic structure variations proposed to give rise to biphilic reactions at phosphorus. These data are presented alongside experimentally referenced electronic structure calculations that reveal nontrigonal structures predicted to further enhance biphilic reactivity in σ3-P ligands and catalysts., NIH NIGMS (Grant GM114547), NSF (Grant CHE-1724505)

Radionuclides find widespread use in medical technologies for treating and diagnosing disease. Among successful and emerging radiotherapeutics, 119Sb has unique potential in targeted therapeutic applications for low-energy electron-emitting isotopes. Unfortunately, developing 119Sb-based drugs has been slow in comparison to other radionuclides, primarily due to limited accessibility. Herein is a production method that overcomes this challenge and expands the available time for large-scale distribution and use. Our approach exploits high flux and fluence from high-energy proton sources to produce longer lived 119mTe. This parent isotope slowly decays to 119Sb, which in turn provides access to 119Sb for longer time periods (in comparison to direct 119Sb production routes). We contribute the target design, irradiation conditions, and a rapid procedure for isolating the 119mTe/119Sb pair. To guide process development and to understand why the procedure was successful, we characterized the Te/Sb separation using Te and Sb K-edge X-ray absorption spectroscopy. The procedure provides low-volume aqueous solutions that have high 119mTe—and consequently 119Sb—specific activity in a chemically pure form. This procedure has been demonstrated at large-scale (production-sized, Ci quantities), and the product has potential to meet stringent Food and Drug Administration requirements for a 119mTe/119Sb active pharmaceutical ingredient., A large-scale production method for 119mTe and 119Sb from an Sb target is described, with X-ray absorption spectroscopy measurements providing insight into the success of the chemical separations.

Borenium ions (i.e., three-coordinate boron cations) are known to promote a wide variety of stoichiometric and catalytic reactions because of their high Lewis acidity. As demonstrated by the growing number of chemically reactive borane ligands, there is considerable interest in developing ligands with highly electrophilic boron sites that promote multisite reactivity in metal complexes. However, there are currently few examples of ligand-centered borenium ions, especially with ligands that form coordination complexes with a wide range of metals. Here we report borenium-like reactivity on a highly versatile diphosphine ligand. Treating (

Diphosphines are highly versatile ancillary ligands in coordination chemistry and catalysis because their structures and donor–acceptor properties can vary widely depending on the substituents atta...

Phosphorus K-edge X-ray absorption spectroscopy (XAS) is a highly effective experimental method for investigating metal-phosphorus bonding and electronic structure. Here, we provide a comprehensive...

PK-edge X-ray absorption near-edge structure (XANES) spectroscopy is a powerful method for analyzing the electronic structure of organic and inorganic phosphorus compounds. Like all XANES experiments, PK-edge XANES requires well defined and readily accessible calibration standards for energy referencing so that spectra collected at different beamlines or under different conditions can be compared. This is especially true for ligandK-edge X-ray absorption spectroscopy, which has well established energy calibration standards for Cl (Cs2CuCl4) and S (Na2S2O3·5H2O), but not neighboring P. This paper presents a review of common PK-edge XANES energy calibration standards and analysis of PPh4Br as a potential alternative. The PK-edge XANES region of commercially available PPh4Br revealed a single, highly resolved pre-edge feature with a maximum at 2146.96 eV. PPh4Br also showed no evidence of photodecomposition when repeatedly scanned over the course of several days. In contrast, we found that PPh3rapidly decomposes under identical conditions. Density functional theory calculations performed on PPh3and PPh4+revealed large differences in the molecular orbital energies that were ascribed to differences in the phosphorus oxidation state (IIIversusV) and molecular charge (neutralversus+1). Time-dependent density functional theory calculations corroborated the experimental data and allowed the spectral features to be assigned. The first pre-edge feature in the PK-edge XANES spectrum of PPh4Br was assigned to P 1s → P-C π* transitions, whereas those at higher energy were P 1s → P-C σ*. Overall, the analysis suggests that PPh4Br is an excellent alternative to other solid energy calibration standards commonly used in PK-edge XANES experiments.

Here we describe the synthesis, structures, and reactivity of Ru complexes containing a triaryl, redox-active S2N2 ligand derived from o-phenylenediamine and thioanisole subunits. The coordination chemistry of N,N′-bis[2-(methylthio)phenyl]-1,2-diaminobenzene [H2(MeSNNSMe)] was established by treating RuCl2(PPh3)3 with H2(MeSNNSMe) to yield {Ru[H2(MeSNNSMe)]Cl(PPh3)}Cl (1). Coordinated H2(MeSNNSMe) was sequentially deprotonated to form Ru[H(MeSNNSMe)]Cl(PPh3) (2) followed by the five-coordinate, square pyramidal complex Ru(MeSNNSMe)(PPh3) (3). Single-crystal X-ray diffraction (XRD) studies revealed that the ligand structurally rearranged around the metal at each deprotonation step to conjugate the adjacent aryl groups with the o-phenylenediamine backbone. Deprotonation of 2 with NaBH4 or treatment of 3 with BH3·tetrahydrofuran (THF) yielded Ru[(μ-H)BH2](MeSNNSMe)(PPh3) (5) with BH3 bound across a Ru–N bond in a metal–ligand cooperative fashion. The cyclic voltammogram of 3 in THF revealed three redox even...

The synthesis, coordination chemistry, and reactivity of two diphosphines containing the cyclic triaminoborane 1,8,10,9-triazaboradecalin (TBD) are described. To evaluate the ligand-centered reactivity of PhTBDPhos and iPrTBDPhos, the complexes (PhTBDPhos)MCl2 and (iPrTBDPhos)MCl2, where M = Ni and Pd, were prepared and characterized by elemental analysis, multinuclear NMR spectroscopy (1H, 13C, 31P, and 11B), and single-crystal X-ray diffraction (XRD). Despite very low boron Lewis acidity in the TBD backbone, (PhTBDPhos)NiCl2 (1) and (PhTBDPhos)PdCl2 (3) react with H2O, alcohols, and hydrated fluoride reagents in the presence of NEt3 to yield trans H–O or H–F addition across the bridgehead N–B bond. In contrast, iPrTBDPhos shows no appreciable reactivity when bound to NiCl2 (2) and PdCl2 (4), which is attributed to the sterically-bulky isopropyl substituents blocking substrate access to boron in the TBD backbone. The new complexes {[(PhTBDPhos-H2O)Ni]2(μ-OH)2}Cl2 (5), {[(PhTBDPhos-H2O)Pd]2(μ-OH)2}Cl2 (6), (PhTBDPhos-MeOH)NiCl2 (7), (PhTBDPhos-MeOH)PdCl2 (8), (PhTBDPhos-C3H5OH)PdCl2 (9), and {[(PhTBDPhos-HF)Ni]2(μ-OH)2}Cl2 (10) were isolated, and all but 6 were structurally characterized by single-crystal XRD. Multinuclear NMR studies revealed that isolated, crystallographically-authenticated samples of 5–9 lose ligand-bound water or alcohol with reappearance of starting materials 1 and 3 when dissolved in NMR solvents. Addition of NEt3 attenuated the water and alcohol loss from 5–9 to allow 1H, 13C, 31P, and 11B NMR data to be collected for all the compounds, confirming the determined structures. Additional reactivity experiments with NaOMe and fluoride reagents suggested that participation of the bridgehead nitrogen in the TBD backbone is important for promoting reactivity at boron when PhTBDPhos is bound to Ni and Pd. The term “cooperative ligand-centered reactivity” (CLR) is proposed to define chemical reactions that appear to require participation of more than one atom on the ligand, such as those reported here.

The continued development of redox-active ligands requires an understanding as to how ligand modifications and related factors affect the locus of redox activity and spin density in metal complexes. Here we describe the synthesis, characterization, and electronic structure of nickel complexes containing triaryl NNNN (

In this Forum Article, we review the development of chelating borohydride ligands called aminodiboranates (H3BNR2BH3–) and phosphinodiboranates (H3BPR2BH3–) for the synthesis of trivalent f-element...

Bond distance is a common structural metric used to assess changes in metal-ligand bonds, but it is not clear how sensitive changes in bond distances are with respect to changes in metal-ligand covalency. Here we report ligand K-edge XAS studies on Ni and Pd complexes containing different phosphorus(III) ligands. Despite the large number of electronic and structural permutations, P K-edge pre-edge peak intensities reveal a remarkable correlation that spectroscopically quantifies the linear interdependence of covalent M-P σ bonding and bond distance. Cl K-edge studies conducted on many of the same Ni and Pd compounds revealed a poor correlation between M-Cl bond distance and covalency, but a strong correlation was established by analyzing Cl K-edge data for Ti complexes with a wider range of Ti-Cl bond distances. Together these results establish a quantitative framework to begin making more accurate assessments of metal-ligand covalency using bond distances from readily-available crystallographic data.

We report the small-scale synthesis, isolated yield, single-crystal X-ray structure

Here we report a new class of homoleptic f-element borohydride complexes called phosphinodiboranates. Treating UI3(1,4-dioxane)1.5, NdI3, or ErI3, with three equiv. of K(H3BPtBu2BH3) in Et2O yielded M2(H3BPtBu2BH3)6, where M = U, Nd, and Er. All three complexes form solid-state dimers, but exist as mixtures of monomers and dimers in solution.

Despite the long-standing use of phosphine and diphosphine ligands in coordination chemistry and catalysis, questions remain as to their effects on metal-ligand bonding in transition metal complexes. Here we report ligand K-edge XAS, DFT, and TDDFT studies aimed at quantifying the impact of coordination geometry, diphosphine bite angle, and phosphine trans influence on covalency in M-P and M-Cl bonds. A series of four-coordinate NiCl2 and PdCl2 complexes containing PPh3 or Ph2P(CH2)nPPh2, where n = 1 (dppm), 2 (dppe), 3 (dppp), and 4 (dppb), was analyzed. The XAS data revealed that changing the coordination geometry from tetrahedral in Ni(PPh3)2Cl2 (1) to square planar in Ni(dppe)Cl2 (2) more than doubles the intensity of pre-edge features assigned to Ni-P and Ni-Cl 1s → σ* transitions. By way of comparison, varying the diphosphine in Pd(dppm)Cl2 (4), Pd(dppp)Cl2 (6), and Pd(dppb)Cl2 (7) yielded Pd-P 1s → σ* transitions with identical intensities, but a 10% increase was observed in the P K-edge XAS spectrum of Pd(dppe)Cl2 (5). A similar observation was made when comparing Ni(dppe)Cl2 (2) to Ni(dppp)Cl2 (3), and DFT and TDDFT calculations corroborated XAS results obtained for both series. Comparison of the spectroscopic and theoretical results to the diphosphine structures revealed that changes in M-P covalency were not correlated to changes in bite angles or coordination geometry. As a final measure, P and Cl K-edge XAS data were collected on trans-Pd(PPh3)2Cl2 (8) for comparison to the cis diphosphine complex Pd(dppe)Cl2 (5). Consistent with phosphine's stronger trans influence compared to chloride, a 35% decrease in the intensity of the Pd-P 1s → σ* pre-edge feature and a complementary 34% increase in Pd-Cl 1s → σ* feature was observed for 8 (trans) compared to 5 (cis). Overall, the results reveal how coordination geometry, ligand arrangement, and diphosphine structure affect covalent metal-phosphorus and metal-chloride bonding in these late transition metal complexes.

New members of the dithiophosphinic acid family of potential actinide extractants were prepared: heterocyclic 2,2'-biphenylenedithiophosphinic acids of stoichiometry HS2P(R2C12H6) (R = H or (t)Bu). The time- and atom-efficient syntheses afforded multigram quantities of pure HS2P(R2C12H6) in reasonable yields (∼60%). These compounds differed from other diaryldithiophosphinic acid extractants in that the two aryl groups were connected to one another at the ortho positions to form a 5-membered dibenzophosphole ring. These 2,2'-biphenylenedithiophosphinic acids were readily deprotonated to form S2P(R2C12H6)(1-) anions, which were crystallized as salts with tetraphenylpnictonium cations (ZPh4(1+); Z = P or As). Coordination chemistry between [S2P((t)Bu2C12H6)](1-) and [S2P(C6H5)2](1-) with U, Np, and Pu was comparatively investigated. The results showed that dithiophosphinate complexes of U(IV) and Np(IV) were redox stable relative to those of U(III), whereas reactions involving Pu(IV) gave intractable material. For instance, reactions involving U(IV) and Np(IV) generated An[S2P((t)Bu2C12H6)]4 and An[S2P(C6H5)2]4 whereas reactions between Pu(IV) and [S2P(C6H5)2](1-) generated a mixture of products from which we postulated a transient Pu(III) species based on UV-Vis spectroscopy. However, the trivalent Pu[S2P(C6H5)2]3(NC5H5)2 compound is stable and could be isolated from reactions between [S2P(C6H5)2](1-) and the trivalent PuI3(NC5H5)4 starting material. Attempts to synthesize analogous trivalent compounds with U(III) provided the tetravalent U[S2P(C6H5)2]4 oxidation product.

P K-edge X-ray absorption near-edge structure (XANES) spectroscopy is a powerful method for analyzing the electronic structure of organic and inorganic phosphorus compounds. Like all XANES experiments, P K-edge XANES requires well defined and readily accessible calibration standards for energy referencing so that spectra collected at different beamlines or under different conditions can be compared. This is especially true for ligand K-edge X-ray absorption spectroscopy, which has well established energy calibration standards for Cl (Cs

The synthesis and characterization of the new arsenic dithiocarbamate complex As[S2CNPh2]3 and three new phosphonium dithiocarbamates [PPh4][S2CNR2], where R2 = Et2, (CH2)5 and Ph2, are reported. As[S2CNPh2]3 was prepared by treating AsI3 with three equivalents of NaS2CNPh2 in a 2:1 mixture of H2O and EtOH. The precipitate that formed was recrystallized from hot toluene to yield yellow prisms of As[S2CNPh2]3 suitable for single-crystal X-ray diffraction (XRD). Attempts to prepare the known compound As[S2CN(CH2)5]3 using a similar route resulted in a mixture of As[S2CN(CH2)5]3 and the mixed iodide species As[S2CN(CH2)5]2I. Single-crystals of both compounds were isolated from concentrated Et2O/CHCl3 solutions and their structures are described here for the first time. [PPh4][S2CNR2] salts were prepared for comparison to arsenic dithiocarbamates by metathesis reactions with PPh4Br and NaS2CNR2 in acetonitrile. All three salts could be obtained in high-purity from MeCN/Et2O solutions and crystal structures of [PPh4][S2CNEt2] and [PPh4][S2CN(CH2)5] reveal charge-separated phosphonium cations and dithiocarbamate anions. The five new crystal structures are used to compare dithiocarbamate bond distances and angles in the presence and absence of arsenic. Nuclear magnetic resonance (NMR) spectra, infrared (IR) spectra, microanalyses, and melting points of the compounds are reported.

Understanding the uranium 5f/6d orbital mixing with oxygen 2p valence orbitals in uranium oxides is important for advancing nuclear technology. Unfortunately, U–O orbital mixing is difficult to probe experimentally. In this manuscript, U–O bonding is evaluated in U 3 O 8 using O K-edge X-ray absorption spectroscopy (XAS). To confirm that the O K-edge XAS spectra were correct and did not contain contributions from surface contamination, three different sample types were investigated using three unique detection methods. Specifically an epitaxial film of U 3 O 8 deposited on Al 2 O 3 (PAD-U 3 O 8 ) was probed using grazing-incidence fluorescence yield (GIFY) detection, a bulk powder of α-phase U 3 O 8 was analyzed with fluorescence yield (FY) detection at normal incidence, and particles of α-phase U 3 O 8 were studied in transmission mode using a scanning transmission X-ray microscope (STXM). Experimental spectra have been presented in the context of previously published computational results from DFT using the Heyd–Scuseria–Ernzerhof (HSE) screened hybrid functional. Overall, the comparative analyses of PAD-U 3 O 8 and α-phase U 3 O 8 samples enabled identification of unique signatures associated with oxygen 2p orbital mixing with both U V and U VI 5f and 6d valence orbitals.

We describe an example of a new phenomenon: the use of a growth inhibitor to homogenize nucleation and improve the smoothness of a thin film deposited by chemical vapor deposition. For many film–substrate combinations, the rate of nucleation on the substrate is slow relative to the growth rate, a situation that produces a broad distribution of island sizes and a rough surface morphology. We show an example in which this outcome is avoided by directing a second component onto the substrate that has little effect on the nucleation rate but significantly retards the island growth rate. The case studied is the growth of HfB2 films on SiO2 substrates using the chemical vapor deposition precursor Hf(BH4)4 with NH3 as the inhibitor. The addition of the inhibitor increases the island density at coalescence by 50× and decreases the roughness by 10× to the subnm range. We suggest that the use of inhibitors to homogenize nucleation may be applicable to other film–substrate combinations.

Correction for ‘Ligand K-edge XAS, DFT, and TDDFT analysis of pincer linker variations in Rh(i) PNP complexes: reactivity insights from electronic structure’ by Jason M. Keith, Scott R. Daly, et al., Dalton Trans., 2016, 45, 9774–9785.

N,N-Dimethylaminodiboranate complexes with praseodymium, samarium, erbium, and uranium, which are potential chemical vapor deposition precursors for the deposition of metal boride and oxide thin films, have been investigated by DFT guided by field-ionization mass spectros- copy experiments. The calculations indicate that the volatilities of these complexes are correlated with the M−H bond strengths as determined by Mayer bond order analysis. The geometries of the gas-phase monomeric, dimeric, and trimeric species seen in field-ionization mass spectroscopy experiments were identified using DFT calculations, and the relative stabilities of these oligomers were assessed to understand how the lanthanide aminodiboranates depolymerize to their respective volatile forms during sublimation.

The dithiophosphinic acid HS(2)P(o-CF(3)C(6)H(4))(2) is known to exhibit exceptionally high extraction selectivities for trivalent minor actinides (Am and Cm) in the presence of trivalent lanthanides. To generate insight that may account for this observation, a series of [PPh(4)][S(2)PR(2)] complexes, where R = Me (1), Ph (2), p-CF(3)C(6)H(4) (3), m-CF(3)C(6)H(4) (4), o-CF(3)C(6)H(4) (5), o-MeC(6)H(4) (6), and o-MeOC(6)H(4) (7), have been investigated using sulfur K-edge X-ray absorption spectroscopy (XAS) and time-dependent density functional theory (TDDFT). The experimental analyses show distinct features in the spectrum of S(2)P(o-CF(3)C(6)H(4))(2)(-) (5) that are not present in the spectrum of 4, whose conjugate acid exhibits reduced selectivity, or in the spectra of 2 and 3, which are anticipated to have even lower separation factors based on previous studies. In contrast, the spectrum of 5 is similar to those of 6 and 7, despite the significantly different electron-donating properties associated with the o-CF(3), o-Me, and o-OMe substituents. The TDDFT calculations suggest that the distinct spectral features of 5-7 result from steric interactions due to the presence of the ortho substituents, which force the aryl groups to rotate around the P-C bonds and reduce the molecular symmetry from approximately C(2v) in 2-4 to C(2) in 5-7. As a consequence, the change in aryl group orientation appears to make the ortho-substituted S(2)PR(2)(-) anions "softer" extractants compared with analogous Ph-, p-CF(3)C(6)H(4)-, and m-CF(3)C(6)H(4)-containing ligands (2-4) by raising the energies of the sulfur valence orbitals and enhancing orbital mixing between the S(2)P molecular orbitals and the aryl groups bound to phosphorus. Overall, we report that sulfur K-edge XAS experiments and TDDFT calculations reveal unique electronic properties of the S(2)P(o-CF(3)C(6)H(4))(2)(-) anion in 5. These results correlate with the special extraction properties associated with HS(2)P(o-CF(3)C(6)H(4))(2), and suggest that ligand K-edge XAS and TDDFT can be used to guide separation efforts relevant to advanced fuel cycle development.

New lanthanide N,N-dimethylaminodiboranate (DMADB) complexes of stoichiometry Ln(H(3)BNMe(2)BH(3))(3) and Ln(H(3)BNMe(2)BH(3))(3)(thf) have been prepared, where Ln = yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, and lutetium, except that isolation of the desolvated complexes proved difficult for Eu and Yb. The tetrahydrofuran (thf) complexes are all monomeric, and most of them adopt 13-coordinate structures in which each DMADB group chelates to the metal center by means of four B-H···Ln bridges (each BH(3) group is κ(2)H; i.e., forms two B-H···Ln interactions). For the smallest three lanthanides, Tm, Yb, and Lu, the metal center is 12 coordinate because one of the DMADB groups chelates to the metal center by means of only three B-H···Ln bridges. The structures of the base-free Ln(H(3)BNMe(2)BH(3))(3) complexes are highly dependent on the size of the lanthanide ions: as the ionic radius decreases, the coordination number decreases from 14 (Pr) to 13 (Sm) to 12 (Dy, Y, Er). The 14-coordinate complexes are polymeric: each metal center is bound to two chelating DMADB ligands and to two "ends" of two ligands that bridge in a Ln(κ(3)H-H(3)BNMe(2)BH(3)-κ(3)H)Ln fashion. In the 13-coordinate complexes, all three DMADB ligands are chelating, but the metal atom is also coordinated to one hydrogen atom from an adjacent molecule. The 12-coordinate complexes adopt a dinuclear structure in which each metal center is bound to two chelating DMADB ligands and to two ends of two ligands that bridge in a Ln(κ(2)H-H(3)BNMe(2)BH(3)-κ(2)H)Ln fashion. The complexes react with water, and the partial hydrolysis product [La(H(3)BNMe(2)BH(3))(2)(OH)](4) adopts a structure in which the lanthanum and oxygen atoms form a distorted cube; each lanthanum atom is connected to three bridging hydroxyl groups and to two chelating DMADB ligands. One B-H bond of each chelating DMADB ligand forms a bridge to an adjacent metal center. Field ionization MS data, melting and decomposition points, thermogravimetric data, and NMR data, including an analysis of the paramagnetic lanthanide induced shifts (LIS), are reported for all of the complexes. The Ln(H(3)BNMe(2)BH(3))(3) compounds, which are highly volatile and sublime at temperatures as low as 65 °C in vacuum, are suitable for use as chemical vapor deposition (CVD) and atomic layer deposition (ALD) precursors to thin films.

The reaction of uranium tetrachloride, UCl4, with sodium N,N-dimethylaminodiboranate, Na(H3BNMe2BH3), in refluxing 1,2-dimethoxyethane (dme) yields small amounts of a new complex, which we formulate as (μ-oxo)hexakis(tetrahydroborato)bis(1,2-dimethoxyethane)diuranium(IV), toluene solvate, U2(μ-O)(BH4)6(dme)2·C7H8, 1. Most likely, the formation of BH4− groups from H3BNMe2BH3− occurs with the elimination of [Me2NBH2]2, and the formation of the oxo group involves adventitious hydrolysis. Each uranium center in 1 adopts a fac octahedral geometry (counting the BH4− groups as occupying one coordination site); the bridging oxygen atom and the two coordinated oxygen atoms of the dme ligand occupy positions trans to the three BH4− groups. The hydrogen atom positions were located in the electron density difference maps and reveal that all three BH4− groups are bound in a κ3H fashion. The U⋯B distances to the two BH4− groups that are cis to the bridging oxygen atom are 2.574(6) and 2.584(6) A, whereas the U⋯B distance of 2.635(7) A to the BH4− group that is trans to the bridging oxygen is distinctly longer. Thus, the bridging oxygen atom exerts a noticeable trans influence. The crystallographic and 1H NMR data strongly suggest that the previously reported uranium hydride complex U2(μ-H)2(BH4)6(dme)2 should be reformulated as this oxo complex U2(μ-O)(BH4)6(dme)2.