Ammonium violurate: a compact structure with extensive hydrogen bonding in three dimensions

The title compound [systematic name: ammonium pyrimidine‐2,4‐5,6(1H,3H)‐tetrone 5‐oximate], NH₄⁺·C₄H₂N₃O₄⁻, crystallizes from water in the triclinic space group P and is ismorphous with a known rubidium complex [Gillier (1965). Bull. Soc. Chim. Fr. pp. 2373–2384]. The principal feature of the structure is hydrogen bonding; each ammonium H atom acts as a bifurcated donor and three of the four violurate O atoms are bifurcated acceptors, with the fourth acting as a trifurcated acceptor. The pattern of hydrogen bonding around the cation is very similar to the rubidium coordination environment in the related structure. The violurate anions pack as hydrogen‐bonded crinkled tapes, which are linked and separated by the ammonium cations to give a compact three‐dimensional structure.     

Iron-catalysed alkene and heteroarene H/D exchange by reversible protonation of iron-hydride intermediates

C–H functionalisation reactions offer a sustainable method for molecular construction and diversification. These reactions however remain dominated by precious metal catalysis. While significant interest in iron-catalysed C–H activation reactions has emerged, the isolation, characterisation and mechanistic understanding of these processes remain lacking. Herein the iron-catalysed C(sp²)–H bond hydrogen/deuterium exchange reaction using CD₃OD is reported for both heterocycles and, for the first time, alkenes (38 examples). Isolation and characterisation, including by single-crystal X-ray diffraction, of the key iron-aryl and iron-alkenyl C–H metallation intermediates provided evidence for a reversible protonation of the active iron hydride catalyst. Good chemoselectivity was observed for both substrate classes. The developed procedure is orthogonal to previous iron-catalysed H/D exchange methods which used C₆D₆, D₂, or D₂O as the deuterium source, and uses only bench-stable reagents, including the iron(ii) pre-catalyst. Further, a new mechanism of iron-hydride formation is reported in which β-hydride elimination from an alcohol generates the iron hydride. The ability to produce, isolate and characterise the organometallic products arising from C–H activation presents a basis for future discovery and development.

The iron-catalysed C(sp²)–H bond H/D exchange reaction using CD₃OD is reported for both heterocycles and alkenes. Characterisation of the key C–H metallation intermediates provided evidence for reversible protonation of the iron hydride catalyst.     

Characterization of the Zwitterionic Intermediate in 1,1‐Carboboration of Alkynes

The reaction of a Lewis acidic borane with an alkyne is a key step in a diverse range of main group transformations. Alkyne 1,1‐carboboration, the Wrackmeyer reaction, is an archetypal transformation of this kind. 1,1‐Carboboration has been proposed to proceed through a zwitterionic intermediate. We report the isolation and spectroscopic, structural and computational characterization of the zwitterionic intermediates generated by reaction of B(C₆F₅)₃ with alkynes. The stepwise reactivity of the zwitterion provides new mechanistic insight for 1,1‐carboboration and wider B(C₆F₅)₃ catalysis. Making use of intramolecular stabilization by a ferrocene substituent, we have characterized the zwitterionic intermediate in the solid state and diverted reactivity towards alkyne cyclotrimerization.     

Hydrazine-mediated cyclization of Ugi products to synthesize novel 3-hydroxypyrazoles

This report discloses a novel concise synthesis of a series of 3-hydroxypyrazoles 5 via a tandem Ugi/debenzylation /hydrazine-mediated cyclization sequence. Herein, n-butyl isocyanide 4b was utilized as an alternative to classical convertible isocyanides enabling high yielding hydrazine-mediated cyclization. Taken together, a novel class of 3-hydroxypyrazoles 5a-5i was synthesized with potential to be of interest in future library enrichment strategies.     

Enantioselective organocatalytic α-sulfenylation of substituted diketopiperazines

The asymmetric organocatalytic α-sulfenylation of substituted piperazine-2,5-diones is reported, with cinchona alkaloids as chiral Lewis bases and electrophilic sulfur transfer reagents. Catalyst loadings, the type of sulfur transfer reagent, temperature, and solvent were investigated in order to optimize the reaction conditions. The effects of ring substitution and the type of catalyst on the yield and enantioselectivity of the reaction are reported.     

An [FeIII34] Molecular Metal Oxide

The dissolution of anhydrous iron bromide in a mixture of pyridine and acetonitrile, in the presence of an organic amine, results in the formation of an [Fe₃₄] metal oxide molecule, structurally characterised by alternate layers of tetrahedral and octahedral Fe^III ions connected by oxide and hydroxide ions. The outer shell of the complex is capped by a combination of pyridine molecules and bromide ions. Magnetic data, measured at temperatures as low as 0.4 K and fields up to 35 T, reveal competing antiferromagnetic exchange interactions; DFT calculations showing that the magnitudes of the coupling constants are highly dependent on both the Fe‐O‐Fe angles and Fe?O distances. The simplicity of the synthetic methodology, and the structural similarity between [Fe₃₄], bulk iron oxides, previous Fe^III–oxo cages, and polyoxometalates (POMs), hints that much larger molecular Fe^III oxides can be made.     

Cosmology with galaxy correlations

In this review, I outline the use of galaxy correlations to constrain cosmological parameters. As with the cosmic microwave background (CMB), the density of dark and baryonic matter imprints important scales on the fluctuations of matter and thus the clustering of galaxies, e.g., the particle horizon at matter-radiation equality and the sound horizon at recombination. Precision measurements of these scales from the baryon acoustic oscillations (BAO) and the large scale shape of the power spectrum of galaxy clustering provide constraints on Ω _m h ². Recent measurements from the Sloan Digital Sky Survey (SDSS) and 2dF Galaxy Redshift Survey (2dFGRS) strongly suggest that Ω _m < 0.3. This forms the basic evidence for a flat Universe dominated by a Cosmological Constant (Λ) today (when combined with results from the CMB and supernova surveys). Further evidence for this cosmological model is provided by the late-time Integrated Sachs–Wolfe (ISW) effect, which has now been detected using a variety of tracers of the large scale structure in the Universe out to redshifts of z > 1. The ISW effect also provides an opportunity to discriminate between Λ, dynamical dark energy models and the modification of gravity on large scales.     

Maximizing Coordination Capsule–Guest Polar Interactions in Apolar Solvents Reveals Significant Binding

Guest encapsulation underpins the functional properties of self‐assembled capsules yet identifying systems capable of strongly binding small organic molecules in solution remains a challenge. Most coordination capsules rely on the hydrophobic effect to ensure effective solution‐phase association. In contrast, we show that using non‐interacting anions in apolar solvents can maximize favorable interactions between a cationic Pd₂L₄ host and charge‐neutral guests resulting in a dramatic increase in binding strength. With quinone‐type guests, association constants in excess of 10⁸ m ^?1 were observed, comparable to the highest previously recorded constant for a metallosupramolecular capsule. Modulation of optoelectronic properties of the guests was also observed, with encapsulation either changing or switching‐on luminescence not present in the bulk phase.     

Cluster carbonyls of the [Re(6)(mu(3)-Se)(8)](2+) core: synthesis, structural characterization, and computational analysis

The reactions of the previously reported cluster complexes [Re(6)(mu(3)-Se)(8)(PEt(3))(5)I]I, trans-[Re(6)(mu(3)-Se)(8)(PEt(3))(4)I(2)], and cis-[Re(6)(mu(3)-Se)(8)(PEt(3))(4)I(2)] with the [Re(6)(mu(3)-Se)(8)](2+) core with CO in the presence of AgSbF(6) afforded the corresponding cluster carbonyls [Re(6)(mu(3)-Se)(8)(PEt(3))(5)(CO)][SbF(6)](2) (), trans-[Re(6)(mu(3)-Se)(8)(PEt(3))(4)(CO)(2)][SbF(6)](2) (), and cis-[Re(6)(mu(3)-Se)(8)(PEt(3))(4)(CO)(2)][SbF(6)](2) (). Infrared spectroscopy indicated weakening of the bond in CO, suggesting the existence of backbonding between the cluster core and the CO ligand(s). Electrochemical studies focusing on the reversible, one-electron oxidation of the cluster core revealed a large increase in the oxidation potential upon going from the acetonitrile derivatives to their carbonyl analogs, consistent with the depleted electron density of the cluster core upon CO ligation. Disparities between the IR spectra and oxidation potential between and indicate that electronic differences exist between sites trans and cis to the location of a ligand of interest. The active role played by the Se atoms in influencing the cluster-to-CO bonding interactions is suggested through this result and density functional (DF) computational analysis. The computations indicate that molecular orbitals near the HOMO account for backbonding interactions with a high percentage of participation of Se orbitals.     

Pedagogical challenges in making mathematics relevant for Indigenous Australians

After the invasion and occupation of their land by Europeans, Indigenous Australians were expected to benefit from a Western education system based on that of the dominant Europeans. Gradually educators realized that Aboriginal children learn differently and that Indigenous culture and pedagogy has validity and strength. Of course, educators also need to be acutely aware of the diversity of Indigenous cultures in Australia and that there is not a monolithic sense of Aboriginal identity or Aboriginal pedagogy. Dispossession and alienation, poor health and few employment opportunities must also affect educational interest, attendance, application and performance. In this paper the characteristics of Indigenous learners are examined and pedagogical strategies to assist in both students' learning and teachers' delivery are explored. The message conveyed in this paper has particular relevance for teaching mathematics to Aboriginal learners. It is also of considerable value in teaching mathematics to nonAboriginal students, in Australia and elsewhere.