Interpretation of europium(III) spectra

This review focuses on key aspects of the thermal decomposition of multinary or mixed hydride materials, with a particular emphasis on the rational control and chemical tuning of the strategically important thermal decomposition temperature of such hydrides, Tdec. An attempt is also made to predict the thermal stability of as-yet unknown, elusive or even unknown hydrides. The future of a particularly promising class of materials for hydrogen storage, namely the catalytically enhanced complex metal hydrides, is discussed. The predictions are supported by thermodynamics considerations, calculations derived from molecular orbital (MO) theory and backed up by simple chemical insights and intuition.

Thermal decomposition of the non-interstitial hydrides for the storage and production of hydrogen.

Non-platinum chemotherapeutic metallopharmaceuticals.

ion of a chloride ligand from the dysprosium metallocene [(Cpttt)2DyCl] (1Dy Cpttt=1,2,4-tri(tert-butyl)cyclopentadienide) by the triethylsilylium cation produces the first base-free rare-earth metallocenium cation [(Cpttt)2Dy]+ (2Dy) as a salt of the non-coordinating [B(C6F5)4]− anion. Magnetic measurements reveal that [2Dy][B(C6F5)4] is an SMM with a record anisotropy barrier up to 1277 cm−1 (1837 K) in zero field and a record magnetic blocking temperature of 60 K, including hysteresis with coercivity. The exceptional magnetic axiality of 2Dy is further highlighted by computational studies, which reveal this system to be the first lanthanide SMM in which all low-lying Kramers doublets correspond to a well-defined MJ value, with no significant mixing even in the higher doublets.

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A Dysprosium Metallocene Single-Molecule Magnet Functioning at the Axial Limit.

Cation-π interaction: its role and relevance in chemistry, biology, and material science.

Ligand influences on structure and reactivity in organoalkaline earth chemistry

Solvent-based syntheses have long been normative in all areas of chemistry, although mechanochemical methods (specifically grinding and milling) have been used to good effect for decades in organic, and to a lesser but growing extent, inorganic coordination chemistry. Organometallic synthesis, in contrast, represents a relatively underdeveloped area for mechanochemical research, and the potential benefits are considerable. From access to new classes of unsolvated complexes, to control over stoichiometries that have not been observed in solution routes, mechanochemical (or ‘M-chem’) approaches have much to offer the synthetic chemist. It has already become clear that removing the solvent from an organometallic reaction can change reaction pathways considerably, so that prediction of the outcome is not always straightforward. This Perspective reviews recent developments in the field, and describes equipment that can be used in organometallic synthesis. Synthetic chemists are encouraged to add mechanochemical methods to their repertoire in the search for new and highly reactive metal complexes and novel types of organometallic transformations.

Advances in organometallic synthesis with mechanochemical methods

Synthesis and crystallographic characterization of an unsolvated, monomeric samarium bis(pentamethylcyclopentadienyl) organolanthanide complex, (C5Me5)2Sm

Timothy P. Hanusa

Papers

Ligand influences on structure and reactivity in organoalkaline earth chemistry

Advances in organometallic synthesis with mechanochemical methods

Synthesis and crystallographic characterization of an unsolvated, monomeric samarium bis(pentamethylcyclopentadienyl) organolanthanide complex, (C5Me5)2Sm

Synthesis and X-ray crystal structure of bis(pentamethylcyclopentadienyl) complexes of samarium and europium: (C5Me5)2Sm and (C5Me5)2Eu

Non-cyclopentadienyl organometallic compounds of calcium, strontium and barium