Activation of ammonia and hydrazine by electron rich Fe(ii) complexes supported by a dianionic pentadentate ligand platform through a common terminal Fe(iii) amido intermediate

We report the use of electron rich iron complexes supported by a dianionic diborate pentadentate ligand system, B₂Pz₄Py, for the coordination and activation of ammonia (NH₃) and hydrazine (NH₂NH₂). For ammonia, coordination to neutral (B₂Pz₄Py)Fe(ii) or cationic [(B₂Pz₄Py)Fe(iii)]⁺ platforms leads to well characterized ammine complexes from which hydrogen atoms or protons can be removed to generate, fleetingly, a proposed (B₂Pz₄Py)Fe(iii)–NH₂ complex (3_Ar-NH₂). DFT computations suggest a high degree of spin density on the amido ligand, giving it significant aminyl radical character. It rapidly traps the H atom abstracting agent 2,4,6-tri-tert-butylphenoxy radical (ArO˙) to form a C–N bond in a fully characterized product (2_Ar), or scavenges hydrogen atoms to return to the ammonia complex (B₂Pz₄Py)Fe(ii)–NH₃ (1_Ar-NH₃). Interestingly, when (B₂Pz₄Py)Fe(ii) is reacted with NH₂NH₂, a hydrazine bridged dimer, (B₂Pz₄Py)Fe(ii)–NH₂NH₂–Fe(ii)(B₂Pz₄Py) ((1_Ar)₂-NH₂NH₂), is observed at −78 °C and converts to a fully characterized bridging diazene complex, 4_Ar, along with ammonia adduct 1_Ar-NH₃ as it is allowed to warm to room temperature. Experimental and computational evidence is presented to suggest that (B₂Pz₄Py)Fe(ii) induces reductive cleavage of the N–N bond in hydrazine to produce the Fe(iii)–NH₂ complex 3_Ar-NH₂, which abstracts H˙ atoms from (1_Ar)₂-NH₂NH₂ to generate the observed products. All of these transformations are relevant to proposed steps in the ammonia oxidation reaction, an important process for the use of nitrogen-based fuels enabled by abundant first row transition metals.

Synopsis: a highly reactive Fe(iii)–NH₂ complex is generated via activation of ammonia or hydrazine in reactions of relevance to fundamental steps in ammonia oxidation processes mediated by an abundant, first row transition metal.     

Nonparametric Bayesian Modeling for Stochastic Order

In comparing two populations, sometimes a model incorporating stochastic order is desired. Customarily, such modeling is done parametrically. The objective of this paper is to formulate nonparametric (possibly semiparametric) stochastic order specifications providing richer, more flexible modeling. We adopt a fully Bayesian approach using Dirichlet process mixing. An attractive feature of the Bayesian approach is that full inference is available regarding the population distributions. Prior information can conveniently be incorporated. Also, prior stochastic order is preserved to the posterior analysis. Apart from the two sample setting, the approach handles the matched pairs problem, the k-sample slippage problem, ordered ANOVA and ordered regression models. We illustrate by comparing two rather small samples, one of diabetic men, the other of diabetic women. Measurements are of androstenedione levels. Males are anticipated to produce levels which will tend to be higher than those of females.     

Orientational correlations and order in A3C60

A tight-binding method which has been previously applied to study the effect of uncorrelated orientational disorder on conduction-band properties is extended here to the case of systems with long-range order and/or short-range correlations. The density of states and conductivity are not highly sensitive to the specific short-range correlations, so long as the system is not too close to being fully ordered. Hence the strong effects of disorder found previously appear to be robust and should play an important role in the interpretation of normal-state properties of A₃C₆₀.     

The Unexpected Role of SeVI Species in Epoxidations with Benzeneseleninic Acid and Hydrogen Peroxide

Benzeneperoxyseleninic acid has been proposed as the key intermediate in the widely used epoxidation of alkenes with benzeneseleninic acid and hydrogen peroxide. However, it reacts sluggishly with cyclooctene and instead rapidly decomposes in solution to a mixed selenonium–selenonate salt that was identified by X‐ray absorption and ⁷⁷Se NMR spectroscopy, as well as by single crystal X‐ray diffraction. This process includes a selenoxide elimination of the peroxyseleninic acid with liberation of oxygen and additional redox steps. The salt is relatively stable in the solid state, but generates the corresponding selenonic acid in the presence of hydrogen peroxide. The selenonic acid is inert towards cyclooctene on its own; however, rapid epoxidation occurs when hydrogen peroxide is added. This shows that the selenonic acid must first be activated through further oxidation, presumably to the heretofore unknown benzeneperoxyselenonic acid. The latter is the principal oxidant in this epoxidation.