Nitride protonation and NH3 binding versus N–H bond cleavage in uranium nitrides

The conversion of metal nitrides to NH₃ is an essential step in dinitrogen fixation, but there is limited knowledge of the reactivity of nitrides with protons (H⁺). Herein, we report comparative studies for the reactions of H⁺ and NH₃ with uranium nitrides, containing different types of ancillary ligands. We show that the differences in ancillary ligands, leads to dramatically different reactivity. The nitride group, in nitride-bridged cationic and anionic diuranium(iv) complexes supported by –N(SiMe₃)₂ ligands, is resistant toward protonation by weak acids, while stronger acids result in ligand loss by protonolysis. Moreover, the basic –N(SiMe₃)₂ ligands promote the N–H heterolytic bond cleavage of NH₃, yielding a “naked” diuranium complex containing three bridging ligands, a nitride (N³⁻) and two NH₂ ligands. Conversely, in the nitride-bridged diuranium(iv) complex supported by –OSi(O^tBu)₃ ligands, the nitride group is easily protonated to afford NH₃, which binds the U(iv) ion strongly, resulting in a mononuclear U–NH₃ complex, where NH₃ can be displaced by addition of strong acids. Furthermore, the U–OSi(O^tBu)₃ bonds were found to be stable, even in the presence of stronger acids, such as NH₄BPh₄, therefore indicating that –OSi(O^tBu)₃ supporting ligands are well suited to be used when acidic conditions are required, such as in the H⁺/e⁻ mediated catalytic conversion of N₂ to NH₃.

Ancillary ligands alter the reactivity of U-nitrides with H⁺, relevant to N₂ conversion to NH₃. The amides lead to complete ligand loss and NH₃ activation, while for siloxides, the nitride is protonated to NH₃ leaving the ancillary ligands intact.     

Chaotic Behavior in Slowly Varying Systems of Nonlinear Differential Equations

A technique is developed to find parameter regions of chaotic behavior in certain systems of nonlinear differential equations with slowly varying periodic coefficients. The technique combines previous results on how to find branches of periodic solutions which terminate with a homoclinic orbit and results on how to find chaotic trajectories in the neighborhood of homoclinic trajectories of the autonomous system. The technique is applied to the continuous stirred tank reaction A → B, for which it is shown that a slowly varying periodic flow rate can yield aperiodic temperature fluctuations.     

Secondary Bifurcation in Nonlinear Diffusion Reaction Equations

A set of two coupled nonlinear diffusion reaction equations is studied and the existence of secondary bifurcation is shown. Using the method of two-timing, it is found that diffusion reaction equations of this type can exhibit an exchange of stability between distinct nontrivial solutions. This exchange can provide either a smooth or discontinuous transition between stable solutions, and the nontrivial solutions can be either steady or temporally periodic. This analysis is applied to the model biochemical reaction of Prigogine and the types of secondary bifurcation which occur in this model are classified.     

A Route to Stabilize Uranium(II) and Uranium(I) Synthons in Multimetallic Complexes

Herein, we report the redox reactivity of a multimetallic uranium complex supported by triphenylsiloxide (−OSiPh₃) ligands, where we show that low valent synthons can be stabilized via an unprecedented mechanism involving intramolecular ligand migration. The two- and three-electron reduction of the oxo-bridged diuranium(IV) complex [{(Ph₃SiO)₃(DME)U}₂(μ-O)], 4 , yields the formal “U^II/U^IV”, 5 , and “U^I/U^IV”, 6 , complexes via ligand migration and formation of uranium-arene δ-bond interactions. Remarkably, complex 5 effects the two-electron reductive coupling of pyridine affording complex 7 , which demonstrates that the electron-transfer is accompanied by ligand migration, restoring the original ligand arrangement found in 4 . This work provides a new method for controlling the redox reactivity in molecular complexes of unstable, low-valent metal centers, and can lead to the further development of f-elements redox reactivity.     

A simulation based method to assess inversion algorithms for transverse relaxation data

NMR relaxometry is a very useful tool for understanding various chemical and physical phenomena in complex multiphase systems. A Carr-Purcell-Meiboom-Gill (CPMG) [P.T. Callaghan, Principles of Nuclear Magnetic Resonance Microscopy, Clarendon Press, Oxford, 1991] experiment is an easy and quick way to obtain transverse relaxation constant (T₂) in low field. Most of the samples usually have a distribution of T₂ values. Extraction of this distribution of T₂s from the noisy decay data is essentially an ill-posed inverse problem. Various inversion approaches have been used to solve this problem, to date. A major issue in using an inversion algorithm is determining how accurate the computed distribution is. A systematic analysis of an inversion algorithm, UPEN [G.C. Borgia, R.J.S. Brown, P. Fantazzini, Uniform-penalty inversion of multiexponential decay data, Journal of Magnetic Resonance 132 (1998) 65–77; G.C. Borgia, R.J.S. Brown, P. Fantazzini, Uniform-penalty inversion of multiexponential decay data II. Data spacing, T₂ data, systematic data errors, and diagnostics, Journal of Magnetic Resonance 147 (2000) 273–285] was performed by means of simulated CPMG data generation. Through our simulation technique and statistical analyses, the effects of various experimental parameters on the computed distribution were evaluated. We converged to the true distribution by matching up the inversion results from a series of true decay data and a noisy simulated data. In addition to simulation studies, the same approach was also applied on real experimental data to support the simulation results.     

Characterization of High Voltage Cold Atmospheric Plasma Generation in Sealed Packages as a Function of Container Material and Fill Gas

While numerous experiments have demonstrated the efficacy of high voltage cold atmospheric pressure plasmas (HVCAPs) in sealed packages for microbial inactivation, the influence of the package on the emitted species measured during HVCAP discharge is poorly understood. This study elucidates the impact of the package on plasma generation in sealed packages for four separate gases (ambient air, commercial grade compressed air, a helium/air mixture, and nitrogen) placed in commercially available transparent plastic containers and bags representative of the materials used in the food industry. The container and bag individually reduced emission signal intensity by an average of 63 and 45%, respectively, across the measured wavelengths of 200–1100 nm, demonstrating that they acted as broadband absorbers. Neither the container nor bag caused additional emission lines to appear, indicating no significant effect on the types of species generated. Considering the minimum applied voltage necessary to induce a discharge, the power dissipated by the nitrogen and ambient air plasma generated at 72 ± 3.7 kV RMS were comparable to the compressed dry air discharge generated at 80 ± 3.7 kV RMS. The helium discharge at 37 ± 3.7 kV RMS absorbed approximately 92% more power than these gases. Rotational temperatures ranged from 285 K for helium to 479 K for compressed air. These results indicate that the package impacts the intensity distribution but not the presence of the most dominant peaks, although further studies are required to elucidate the impact on less intense peaks.