The Influence of Phosphorus Substituents on the Structures and Solution Speciation of Trivalent Uranium and Lanthanide Phosphinodiboranates.

Here, we report the mechanochemical synthesis and characterization of homoleptic uranium and lanthanide phosphinodiboranates with isopropyl and ethyl substituents attached to phosphorus. M(H3BPiPr2BH3)3 complexes with M = U, Nd, Sm, Tb, and Er were prepared by ball milling UI3(THF)4, SmBr3, or MI3 with three equivalents of K(H3BPiPr2BH3). M(H3BPEt2BH3)3 with M = U and Nd were prepared similarly using K(H3BPEt2BH3), and the complexes were purified by extraction and crystallization from Et2O or CH2Cl2. Single-crystal XRD studies revealed that all five M(H3BPiPr2BH3)3 crystallize as dimers, despite the significant differences in metal radii across the series. In contrast, Nd(H3BPEt2BH3)3 with smaller ethyl substituents crystallized as a coordination polymer. Crystals of U(H3BPEt2BH3)3 were not suitable for structural analysis, but crystals of U(H3BPMe2BH3)3 isolated in low yield by solution methods were isostructural with Nd(H3BPEt2BH3)3. 1H and 11B NMR studies in C6D6 revealed that all of the complexes form mixtures of monomer and oligomers when dissolved, and the extent of oligomerization was highly dependent on metal radius and phosphorus substituent size. A comprehensive analysis of all structurally characterized uranium and lanthanide phosphinodiboranate complexes reported to date, including those with larger Ph and tBu substituents, revealed that the degree of oligomerization in solution can be correlated to differences in B-P-B angles obtained from single-crystal XRD studies. Density functional theory calculations, which included structural optimizations in combination with conformational searches using tight binding methods, replicated the general experimental trends and revealed free energy differences that account for the different solution and solid-state structures. Collectively, these results reveal how steric changes to phosphorus substituents significantly removed from metal coordination sites can have a significant influence on solution speciation, deoligomerization energies, and the solid-state structure of homoleptic phosphinodiboranate complexes containing trivalent f-metals.

Leveraging Metal and Ligand Reactive Sites for One Pot Reactions: Ligand-Centered Borenium Ions for Tandem Catalysis with Palladium.

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.

Pr(H3BNMe2BH3)3 and Pr(thd)3 as Volatile Carriers for Actinium-225. Deposition of Actinium-Doped Praseodymium Boride Thin Films for Potential Use in Brachytherapy.

Here we show that the praseodymium N,N-dimethylaminodiboranate complex Pr(H3BNMe2BH3)3 and the 2,2,6,6-tetramethylheptane-3,5-dionate complex Pr(thd)3 can serve as volatile carriers for 225Ac. The actinium coordination complexes Ac(H3BNMe2BH3)3 and Ac(thd)3 are the likely species subliming with the carrier material. A sample of 225Ac-doped Pr(H3BNMe2BH3)3 was used to deposit amorphous 225Ac-doped praseodymium boride films on glass and Si(100) at 300 °C. The α emission spectra of the refractory films are well-resolved, suggesting that they could be used as radioactive implants for brachytherapy and related treatments.

Quantifying Variations in Metal-Ligand Cooperative Binding Strength with Cyclic Voltammetry and Redox-Active Ligands.

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 (PPh3 and PCy3) are described. Titration CV studies conducted using BH3·THF with BH3 as a model MLC substrate allowed ΔGMLC to be quantified for each complex. Compared to our base triaryl ligand, increasing π conjugation in the backbone of the redox-active ligand enhanced MLC binding, whereas increasing π conjugation in the flanking groups decreased the MLC binding strength. Structures and spectroscopic data collected for the isolated MLC complexes are also described along with supporting DFT calculations that were used to illuminate electronic factors that likely account for the observed differences in the MLC binding strength. These results demonstrate how redox-active ligands and CV can be used to quantify subtle differences in the MLC binding strength across a series of structurally related complexes with different ligand modifications.

Sodium Aminodiboranates Na(H3BNR2BH3): Structural and Spectroscopic Studies of Steric and Electronic Substituent Effects.

We describe the syntheses of a series of sodium aminodiboranate salts, Na(H3B-NR2-BH3), with different substituents on nitrogen, including sodium salts of the unsubstituted aminodiboranate, H3B-NH2-BH3-, and of the N-substituted anions H3B-NRR'-BH3-, where NRR' = NHMe, NHEt, NH(SiMe3), NEt2, N(i-Pr)2, N(SiMe3)2, NMe(i-Pr), NMe(t-Bu), NMe(SiMe3), and the pyrrolidide and piperidide derivatives NC4H8, NC5H10, and NC5H8-cis-2,6-Me2. The compounds have been characterized by 1H and 11B NMR spectroscopy and IR spectroscopy; crystallographic studies have been carried out for the unsolvated N,N-dimethylaminodiboranate salt Na(H3B-NMe2-BH3) and several sodium aminodiboranate salts in which the sodium ions are solvated with ethers (dioxane, diglyme, tetrahydrofuran, and 12-crown-4) or amines (N,N,N',N'-tetramethylethylenediamine). One of the structures contains a rare example of an ether ligand in which one oxygen atom bridges between two metal ions. General structural and spectroscopic trends as a function of the substituents on nitrogen are discussed.

Quantifying the Influence of Covalent Metal-Ligand Bonding on Differing Reactivity of Trivalent Uranium and Lanthanide Complexes.

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 U3+ and in the absence of competing variables. Here we report a series of dimeric phosphinodiboranate complexes with trivalent f-metals that show how shorter-than-expected U-B distances indicative of increased covalency give rise to measurable differences in solution deoligomerization reactivity when compared to isostructural complexes with similarly sized lanthanides. These results, which are in excellent agreement with supporting DFT and QTAIM calculations, afford rare experimental evidence concerning the measured effect of variations in metal-ligand covalency on the reactivity of trivalent uranium and lanthanide complexes.

Characterizing Polyoxovanadate-Alkoxide Clusters Using Vanadium K-Edge X-Ray Absorption Spectroscopy.

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.

Convenient Syntheses of Trivalent Uranium Halide Starting Materials without Uranium Metal.

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.

Chelating Borohydrides for Lanthanides and Actinides: Structures, Mechanochemistry, and Case Studies with Phosphinodiboranates.

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 complexes. The advantages and history of using mechanochemistry to prepare molecular borohydride complexes are described along with new results demonstrating the mechanochemical synthesis of M2(H3BPtBu2BH3)6, where M = U, Nd, Tb, Er, and Lu (1-5). Multinuclear NMR, IR, and single-crystal X-ray diffraction data are reported for 1-5 alongside complementary density functional theory calculations to reveal differences in their structure and reactivity with and without tetrahydrofuran. The results demonstrate how mechanochemistry can be used to access f-element complexes with chelating borohydrides in improved and reproducible yields, which is an important step toward investigating the properties of lanthanide and actinide phosphinodiboranate complexes with different phosphorus substituents. The relevance of these results is contextualized by a discussion of structural factors known to influence the volatility of f-element borohydrides and applications that require the development of volatile f-element complexes.

Influence of Multisite Metal-Ligand Cooperativity on the Redox Activity of Noninnocent N2S2 Ligands.

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 metal complexes. Despite growing interest in combining ligand-centered chemical and redox reactions for chemical transformations, there are few studies demonstrating how chemically engaging redox active ligands in MLC affects their electrochemical properties when bound to metals. Here we report stepwise changes in the redox activity of model Ru complexes as zero, one, and two BH3 molecules undergo MLC binding with a triaryl noninnocent N2S2 ligand derived from o-phenylenediamine (L1). A similar series of Ru complexes with a diaryl N2S2 ligand with ethylene substituted in place of phenylene (L2) is also described to evaluate the influence of the o-phenylenediamine subunit on redox activity and MLC. Cyclic voltammetry (CV) studies and density functional theory (DFT) calculations show that MLC attenuates ligand-centered redox activity in both series of complexes, but electron transfer is still achieved when only one of the two redox-active sites on the ligands is chemically engaged. The results demonstrate how incorporating more than one multifunctional reactive site could be an effective strategy for maintaining redox noninnocence in ligands that are also chemically reactive and competent for MLC.

The Influence of Redox-Innocent Donor Groups in Tetradentate Ligands Derived from o-Phenylenediamine: Electronic Structure Investigations with Nickel.

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 (1) and SNNS (2) ligands derived from o-phenylenediamine. The tetradentate ligands in 1 and 2 were investigated and compared to those in metal complexes with compositionally similar ligands to determine how ligand-centered redox properties change when redox-active flanking groups are replaced with redox-innocent NMe2 or SMe. A derivative of 2 in which the phenylene backbone was replaced with ethylene (3) was also prepared to interrogate the importance of o-phenylenediamine for ligand-centered redox activity. Cyclic voltammograms collected for 1 and 2 revealed two fully reversible ligand-centered redox events. Remarkably, several quasi-reversible ligand-centered redox waves were also observed for 3 despite the absence of the o-phenylenediamine subunit. Oxidizing 1 and 2 with silver salts containing different counteranions (BF4-, OTf-, NTf2-) allowed the electrochemically generated complexes to be analyzed as a function of different oxidation states using single-crystal X-ray diffraction (XRD), EPR spectroscopy, and S K-edge X-ray absorption spectroscopy. The experimental data are corroborated by DFT calculations, and together, they reveal how the location of unpaired spin density and electronic structure in singly and doubly oxidized salts of 1 and 2 varies depending on the coordinating ability of the counteranions and exogenous ligands such as pyridine.

Quantifying the Interdependence of Metal-Ligand Covalency and Bond Distance Using Ligand K-edge XAS.

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.

Validating the Biphilic Hypothesis of Nontrigonal Phosphorus(III) Compounds.

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.

[Am(C5 Me4 H)3 ]: An Organometallic Americium Complex.

We report the small-scale synthesis, isolated yield, single-crystal X-ray structure, 1 H 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(C5 Me4 H)3 ] (1). This constitutes the first quantitative data on Am-C bonding in a molecular species.

Solid energy calibration standards for P K-edge XANES: electronic structure analysis of PPh4Br.

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 (Cs2CuCl4) and S (Na2S2O3·5H2O), but not neighboring P. This paper presents a review of common P K-edge XANES energy calibration standards and analysis of PPh4Br as a potential alternative. The P K-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 PPh3 rapidly decomposes under identical conditions. Density functional theory calculations performed on PPh3 and PPh4+ revealed large differences in the molecular orbital energies that were ascribed to differences in the phosphorus oxidation state (III versus V) and molecular charge (neutral versus +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 P K-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 P K-edge XANES experiments.

Ligand-Centered Borenium Reactivity in Triaminoborane-Bridged Diphosphine Complexes.

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 (PhTBDPhos)NiCl2 (1) with strong Bronsted acids such as HBF4·Et2O, HOTf, or HNTf2 resulted in fluoride or chloride abstraction from BF4- or NiCl2, respectively, to form trans N-H and B-X bonds on the ligand backbone. HCl addition to the bridgehead N-B bond is reversible, and the reactivity depends on the identity of the supporting counteranions, as observed when treating [(PhTBDPhos)NiCl]2X2, where X = NTf2- (3), OTf- (4), or BArF4- (5), with HCl. The reaction of 4 with HNTf2 instead of HCl yielded NMR evidence of the latent borenium cation in solution and showed how poor nucleophiles such as triflate bind to the borenium ion in the solid state. Remarkably, replacing the chloride ligands in 1 with chelating and less-labile thiolates or catecholates, or changing the phosphorus substituents (phenyl to isopropyl), attenuates the reactivity on the ligand backbone. Density functional theory was used to quantify the reaction free energies, and the theoretical results corroborate the experimental observations. Given the broad utility of diphosphines in homogeneous catalysis and the known benefits of strong Lewis acid promotors in many catalytic reactions, we anticipate that the results will provide new opportunities for dual-site reactivity involving boron ligands and metals.

Measurement of Diphosphine σ-Donor and π-Acceptor Properties in d0 Titanium Complexes Using Ligand K-Edge XAS and TDDFT.

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 attached to phosphorus. Experimental and theoretical methods have been developed to quantify differences in phosphine and diphosphine ligand field strength, but experimentally measuring individual σ-donor and π-acceptor contributions to metal-phosphorus bonding remains a formidable challenge. Here we report P and Cl K-edge X-ray absorption spectroscopy (XAS), density functional theory (DFT), and time-dependent density functional theory (TDDFT) studies of a series of [Ph2P(CH2) nPPh2]TiCl4 complexes, where n = 1, 2, or 3. The d0 metal complexes (Ti4+) revealed both P 1s → Ti-P π and P 1s → Ti-P σ* transitions in the P K-edge XAS spectra, which allowed spectral changes associated with Ti-P σ-bonding and π-backbonding to be evaluated as a function of diphosphine alkane length. DFT and TDDFT calculations were used to assign and quantify changes in Ti-P σ-bonding and π-backbonding. The calculated results for [Ph2P(CH2)2PPh2]TiCl4 were subsequently compared to electronic structure calculations and simulated spectra for [R2P(CH2)2PR2]TiCl4, where R = cyclohexyl or CF3, to evaluate spectral changes as a function of diphosphine ligand field strength. Collectively, our results demonstrate how P K-edge XAS can be used to experimentally measure M-P π-backbonding with a d0 metal and corroborate earlier studies showing that relative changes in covalent M-P σ bonding do not depend solely on changes in diphosphine bite angle.

Impact of Coordination Geometry, Bite Angle, and Trans Influence on Metal-Ligand Covalency in Phenyl-Substituted Phosphine Complexes of Ni and Pd.

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.

Volatile lanthanide complexes with fluorinated heptadentate ligands.

Understanding factors that influence the volatility of lanthanide complexes remains an important goal for applications such as gas-phase f-metal separations and the synthesis of lanthanide-containing thin films. Lanthanide complexes often exhibit volatility differences that depend on the ability of ligands to saturate the lanthanide coordination sphere and attenuate intermolecular bonding in the solid state. This can make it difficult to assess how electronic factors associated with differing ligand substituents influence volatility. Here we describe the synthesis, structures, and thermal properties of a series of volatile lanthanide complexes (Ln = Nd, Er, and Yb) containing N4O3 ligands decorated with different alkyl and fluoroalkyl substituents (CF3, CF2CF2CF3, Me, and tBu). These ligands completely enveloped the tested lanthanides to form monomeric complexes with 7-coordinate distorted capped octahedral coordination geometries, as determined using single-crystal X-ray diffraction. Thermogravimetric analysis and bulk sublimation studies show how metal encapsulation affords complexes with the same volatility regardless of metal size, even with lanthanide ions with significantly different radii such as Nd3+ and Yb3+. Most notably, the results show that increasing ligand fluorination, a strategy often used to increase the volatility of metal complexes, is not always beneficial and can significantly attenuate the volatility of lanthanide complexes depending on location with respect to other substituents in the ligand framework. A pair-wise model based on density functional theory shows that the net intermolecular interactions in the unit cell can still be stronger when fluorination is present. In other words, even if individual interactions between neighboring molecules are weaker, the total number of interactions in the solid arising from the nature of crystal packing is equally important to consider.