Synthesis And Characterization Of (pyNO−)2GaCl: A Redox-Active Gallium Complex

We report the synthesis of a gallium complex incorporating redox-active pyridyl nitroxide ligands. The (pyNO−)2GaCl complex was prepared in 85% yield via a salt metathesis route and was characterized by 1H and 13C NMR spectroscopies, X-ray diffraction, and theory. UV–Vis absorption spectroscopy and electrochemistry were used to access the optical and electrochemical properties of the complex, respectively. Our discussion focuses primarily on a comparison of the gallium complex to the corresponding aluminum derivative and shows that although the complexes are very similar, small differences in the electronic structure of the complexes can be correlated to the identity of the metal

The determinants of election to the United Nations Security Council

This is the author's accepted manuscript. The final publication is available at Springer via http://dx.doi.org/10.1007/s11127-013-0096-4.The United Nations Security Council (UNSC) is the foremost international body responsible for the maintenance of international peace and security. Members vote on issues of global importance and consequently receive perks—election to the UNSC predicts, for instance, World Bank and IMF loans. But who gets elected to the UNSC? Addressing this question empirically is not straightforward as it requires a model that allows for discrete choices at the regional and international levels; the former nominates candidates while the latter ratifies them. Using an original multiple discrete choice model to analyze a dataset of 180 elections from 1970 to 2005, we find that UNSC election appears to derive from a compromise between the demands of populous countries to win election more frequently and a norm of giving each country its turn. We also find evidence that richer countries from the developing world win election more often, while involvement in warfare lowers election probability. By contrast, development aid does not predict election

Equitable representation in councils: theory and an application to the United Nations Security Council

We analyze democratic equity in council voting games (CVGs). In a CVG, a voting body containing all members delegates decision-making to a (time-varying) subset of its members, as describes, e.g., the relationship between the United Nations General Assembly and the United Nations Security Council (UNSC). We develop a theoretical framework for analyzing democratic equitability in CVGs at both the country and region levels, and for different assumptions regarding preference correlation. We apply the framework to evaluate the equitability of the UNSC, and the claims of those who seek to reform it. We find that the individual permanent members are overrepresented by between 21.3 times (United Kingdom) and 3.8 times (China) from a country-level perspective, while from a region perspective Eastern Europe is the most heavily overrepresented region with more than twice its equitable representation, and Africa the most heavily underrepresented. Our equity measures do not preclude some UNSC members from exercising veto rights, however

Concomitant Polymorphism In An Organic Solid: Molecular And Crystal Structure And Intra‐ And Intermolecular Potential Contributions To Tert‐Butyl And Methyl Group Rotation

We investigate the relationship between structure (crystal and molecular) and tert‐butyl and methyl group dynamics in 2‐(tert‐butyl)‐9‐(4‐(tert‐butyl)phenyl)anthracene. Powder and single‐crystal X‐ray diffraction, taken together, show that different polycrystalline samples recrystallized from different solvents have different amounts of at least four polymorphs (crystallites having different crystal structures), of which we have identified three by single crystal X‐ray diffraction. The molecules in the asymmetric units of the different crystal structures differ by the dihedral angle the tert‐butylphenyl group makes with the anthracene moiety. Ab initio electronic structure calculations on the isolated molecule show that very little intramolecular energy is required to change this angle over a range of about 60° which is probably the origin of the concomitant polymorphism (crystals of more than one polymorph in a polycrystalline sample). Solid state 1H nuclear magnetic resonance (NMR) spin‐lattice relaxation experiments support the powder and single‐crystal X‐ray results and provide average NMR activation energies (closely related to rotational barriers) for the rotation of the tert‐butyl groups and their constituent methyl groups. These barriers have both an intramolecular and an intermolecular component. The latter is sensitive to the crystal structure. The intramolecular components of the rotational barriers of the two tert‐butyl groups in the isolated molecule are investigated with ab initio electronic structure calculations

Synthesis and Characterization of a Tripodal Tris(nitroxide) Aluminum Complex and Its Catalytic Activity toward Carbonyl Hydroboration

An aluminum complex of a tripodal tris(nitroxide)-based ligand has been prepared and characterized. The complex has the ability to participate in metal–ligand cooperative catalysis, which has been exploited for the hydroboration of both aldehydes and ketones. This represents new, transition-metal-like reactivity for an earth-abundant metal