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June 10, 2013
ChemPlusChem 6/2013: An Unconventional Anion
New ionic liquids and solid-state electrolytes that incorporate the carbamoylcyano(nitroso)methanide anion have been investigated by Jennifer Pringle et al. The anion can exist in both a syn and anti conformation, contributing to its useful properties such as low viscosity and good conductivity. In their Communication, Honggang Fu et al. describe a combined liquid–liquid interface reaction and the self-assembly of Co clusters to synthesize free-standing ultrathin Co nanosheets, which have ferromagnetic behavior and potential application in catalysis and nanodevices. Among the Full Papers is a report from Koen Binnemans et al. outlining the preparation and isolation of simple silver-containing ionic liquids, which show advantageous electrochemical behavior in terms of electrodeposition of crack-free silver coatings.
Recently Published Articles
- Thermal Activation of Ammonia by Transition-Metal Hydroxide Cations
Dr. Robert Kretschmer, Dr. Maria Schlangen and Prof. Dr. Helmut Schwarz
Article first published online: 19 JUN 2013 | DOI: 10.1002/cplu.201300138
Ready, set, go: The reactions of cationic transition-metal hydroxides, [M(OH)]+, of the first row with ammonia have been studied both experimentally and computationally. With the exception of scandium, all ions investigated react predominantly under NH bond activation (Cr–Ni, Zn), ligand exchange (Ni), or dehydrogenation (Ti, V). Regarding the efficiency, [Co(OH)]+ is taking a strong lead, followed by [Fe(OH)]+ and [Zn(OH)]+. Behind them are [Cr(OD)]+ and [Mn(OH)]+ while [Ti(OH)]+ and [V(OH)]+ ) are just one step behind.
- Mass Spectrometry and Gas-Phase Chemistry of Bismuth–Oxido Clusters
Dominik Sattler, Maik Schlesinger, Prof. Michael Mehring and Prof. Christoph A. Schalley
Article first published online: 17 JUN 2013 | DOI: 10.1002/cplu.201300122
Grow and change: Electrospray ionization (tandem) mass spectrometry was used to investigate the growth of bismuth–oxido clusters in solution, their ligand-exchange reactions, and their fragmentation in the gas phase (see figure). Clusters of different sizes and with different ligand shells were studied to identify typical growth intermediates and to examine dissociation reactions that proceed in the ligand shell as well as within the cluster core.
- Electrospun Spinel LiNi0.5Mn1.5O4 Hierarchical Nanofibers as 5 V Cathode Materials for Lithium-Ion Batteries
Dr. Jun Liu, Wei Liu, Shaomin Ji, Prof. Yichun Zhou, Prof. Peter Hodgson and Dr. Yuncang Li
Article first published online: 13 JUN 2013 | DOI: 10.1002/cplu.201300180
In a spin: LiNi0.5Mn1.5O4 hierarchical nanofibers with diameters of 200–500 nm and lengths of up to several tens of micrometers were synthesized using low-cost starting materials by electrospinning combined with annealing. These nanofibers exhibit a favorable electrochemical performance. At a 0.5 C, they show an initial discharge capacity of 133 mA h g−1 with a capacity retention over 94 % after 30 cycles (see figure).
- A Highly Selective Reaction-Based Two-Photon Probe for Copper(I) in Aqueous Media
Debabrata Maity, Bidyut Sarkar, Sudipta Maiti and Dr. T. Govindaraju
Article first published online: 11 JUN 2013 | DOI: 10.1002/cplu.201300089
Out of the blue: A reaction-based two-photon probe XanCu (see scheme) is reported for the selective detection of Cu+ in reducing aqueous environments. Copper(I)-mediated oxidative benzylic ether (CO) bond cleavage offers “switch-on” detection of the metal ion.
- An Unexpected Pathway for Ligand Substitution in an Aryl Halide Complex of Palladium
Zohrab Ahmadi, Prof. Allen G. Oliver and Assoc. Prof. J. Scott McIndoe
Article first published online: 11 JUN 2013 | DOI: 10.1002/cplu.201300131
A supposed spectator ligand plays a crucial role in a seemingly simple ligand substitution reaction on palladium. Continuous monitoring by ESI-MS reveals all the details of an initial fast displacement of iodide by an incoming phosphine ligand, and of the recoordination of iodide that prompts the displacement of the bidentate ligand actually being substituted. An apparent double substitution and subsequent isomerization can be readily explained by two fast and one slow ligand substitution reactions (see figure).