J. Appl. Cryst.の発刊に際して

1. Advantages of Chemical Redox Agents 878 2. Disadvantages of Chemical Redox Agents 879 C. Potentials in Nonaqueous Solvents 879 D. Reversible vs Irreversible ET Reagents 879 E. Categorization of Reagent Strength 881 II. Oxidants 881 A. Inorganic 881 1. Metal and Metal Complex Oxidants 881 2. Main Group Oxidants 887 B. Organic 891 1. Radical Cations 891 2. Carbocations 893 3. Cyanocarbons and Related Electron-Rich Compounds 894

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Chemical Redox Agents for Organometallic Chemistry

: The unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio. Harmonic force fields are obtained using Density Functional Theory (DFT), MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set. DFT calculations use the Local Spin Density Approximation (LSDA), BLYP, and Becke3LYP (B3LYP) density functionals. Mid-IR spectra predicted using LSDA, BLYP, and B3LYP force fields are of significantly different quality, the B3LYP force field yielding spectra in clearly superior, and overall excellent, agreement with experiment. The MP2 force field yields spectra in slightly worse agreement with experiment than the B3LYP force field. The SCF force field yields spectra in poor agreement with experiment.The basis set dependence of B3LYP force fields is also explored: the 6-31G* and TZ2P basis sets give very similar results while the 3-21G basis set yields spectra in substantially worse agreements with experiment. jg

Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields

The development of microgels/nanogels for drug delivery applications

Advances in copper complexes as anticancer agents.

Investigations of Benzyl and Aryl Palladium Complexes with Pendant Hydroxy Substituents and Their Transformation into Benzolactones on Carbonylation

Replacing a boron vertex in a [BnHn]2− cluster with a smaller atom, e.g. carbon, results in the distance from that atom to the polyhedral centroid being shorter. This forms the basis of a simple but very effective method of distinguishing between B and C atoms in (hetero)carboranes that have been studied crystallographically, the Vertex-to-Centroid Distance (VCD) method. Examples of well-characterised icosahedral and sub-icosahedral closocarboranes, nidocarboranes, icosahedral metallacarboranes and supraicosahedral metallacarboranes are used to illustrate the generality of the VCD method. In this process a number of structures are identified in which the method suggests B/C disorder not previously recognised and some structures in which it appears that a cage C atom has been wrongly assigned. The largest sub-group of heterocarboranes is the family of 3,1,2-MC2B9 compounds, and for these species consideration of Exopolyhedral Ligand Orientation (ELO) can sometimes be used to quickly suggest when a literature structure is suspect in terms of cage C atom positioning. The crystal structure of one such compound, 3,3-NO3-3-PPh3-3,1,2-closo-RhC2B9H11, has been redetermined and the correct location of the cage C atoms established.

The VCD method – a simple and reliable way to distinguish cage C and B atoms in (hetero)carborane structures determined crystallographically

In this paper we report the temperature and pH dependent syntheses and systematic characterization of four new CoII/CoIII and NiII complexes with a pentadentate Schiff base ligand H3L obtained by condensing 1,3,-diaminopropan-2-ol with 2-hydroxyacetophenone in 1 : 2 molar ratio. The room temperature syntheses involving CoII and NiII nitrates and the ligand H3L lead to the isolation of the dinuclear species [Co2L2(H2O)] (1), and the mononuclear complex [Ni(LH)] (3), respectively, whereas refluxing at basic pH leads to the tetranuclear complexes, [CoII2CoIII2L2(μ3-OMe)2(NO3)(H2O)2]NO3·2(H2O) (2), and [Ni4L2(μ3-OMe)2(H2O)2]·2H2O (4). 1 is found to be a simple mono alkoxo-bridged CoIII dinuclear species, whereas 2 and 4 are both rhomb-like tetrameric complexes with double oxo bridges and μ3-methoxo bridges, derived from the methanol solvent, in an open dicubane arrangement. Moreover 2 shows six coordinate ordered CoII and CoIII ions and 4 has both six- and five-coordinate NiII centers. Compound 3 is assigned a tentative mononuclear structure based on IR, UV-Vis spectroscopic, 1H-NMR and ESI mass study results and is supposed to have one NiII center coordinated with a ligand fragment in square planar geometry. The variable temperature magnetic susceptibility study for 2 and 4 is performed which indicate for both 2 and 4 the presence of intracluster dominant ferromagnetic interactions.

Isolation of four new CoII/CoIII and NiII complexes with a pentadentate Schiff base ligand: syntheses, structural descriptions and magnetic studies.

The crystal structure of 3-I-1,2-closo-C2B10H11 reveals that molecules are arranged as infinite head-to-tail zig-zag double chains held together by C–H⋯I hydrogen bonding.

Georgina M. Rosair

Papers

Investigations of Benzyl and Aryl Palladium Complexes with Pendant Hydroxy Substituents and Their Transformation into Benzolactones on Carbonylation

The VCD method – a simple and reliable way to distinguish cage C and B atoms in (hetero)carborane structures determined crystallographically

Isolation of four new CoII/CoIII and NiII complexes with a pentadentate Schiff base ligand: syntheses, structural descriptions and magnetic studies.

Self-assembly of carborane molecules via C–H⋯I hydrogen bonding: the molecular and crystal structures of 3-I-1,2-closo-C2B10H11

Isolation of a nonicosahedral intermediate in the isomerization of an icosahedral metallacarborane