Dalton Transactions

doi: 10.1039/c3dt90141fpmid: N/A

doi: 10.1039/C3DT90141Fpmid: N/A

doi: 10.1039/C3DT90142Dpmid: N/A

doi: 10.1039/c3dt90142dpmid: N/A

doi: 10.1039/C3DT90143Bpmid: N/A

doi: 10.1039/c3dt90143bpmid: N/A

Zangana, Karzan H.; Pineda, Eufemio Moreno; Schnack, Jürgen; Winpenny, Richard E. P.

doi: 10.1039/c3dt52086bpmid: 23970069

Three octanuclear phosphonate clusters, formulated as [Ln8(O3PtBu)6(μ3-OH)2(H2O)2(HOiBu)(O2CtBu)12](NH3iPr)2 (Ln = Gd, Dy and Tb), were synthesised by refluxing a mixture of pivalic acid (HO2CtBu), Ln(NO3)3·6H2O, tert-Butyl phosphonic acid (H2O3PtBu) and isopropylamine (iPrNH2) in isobutyl alcoholiBuOH.

Malyshev, Dimitriy; Boscá, Francisco; Crites, Charles-Oneil L.; Hallett-Tapley, Geniece L.; Netto-Ferreira, José Carlos; Alarcon, Emilio I.; Scaiano, Juan C.

doi: 10.1039/c3dt51167gpmid: 23979588

The size of photochemically-prepared niobium nanoparticles (NbNP) can be controlled by varying the concentration of the photoinitiator in the reaction mixture. The particles, which may be metallic in nature, are readily oxidized upon air exposure to form stable niobium(v) oxide nanoparticles (NbONP) that act as strong Brønsted acids.

Al-Harbi, Ahmed; Rong, Yi; Parkin, Gerard

doi: 10.1039/c3dt52163jpmid: 23986264

Tris(2-pyridonyl)methanes may be synthesized via the reactions of the respective 2-pyridone with CHX3 (X = Cl, Br) and K2CO3 in the presence of [Bun4N]Br, followed by acid-catalyzed isomerization with camphorsulfonic acid. These compounds provide access to a new class of alkyl ligands that feature oxygen donors and are capable of forming metallacarbatranes and a monovalent thallium alkyl compound.

Verma, P. K.; Pathak, P. N.; Bhattacharyya, A.; Prabhu, D. R.; Mohapatra, P. K.

doi: 10.1039/c3dt51825fpmid: 23995412

There are contradicting reports on the thermodynamics of cation–cation interactions (CCIs; inner/outer sphere) involving NpO2+ and UO22+. This paper revisits CCIs of NpO2+ (2 × 10−4 M) under varying conditions such as reaction time, nitric acid (2 × 10−3–4 M HNO3)/uranium (up to 1.2 M) concentrations, and temperature (283–343 K) by spectrophotometric measurements. This study reports for the first time the appearance of a signature peak of Np(iv) (∼964 nm) in addition to NpO2+ (980 nm) and the NpO2+–UO22+ complex (992 nm). For a pure NpO2+ solution at 4 M HNO3, there is a gradual increase in Np(iv) peak intensity with increasing temperature and correspondingly the Np(v) peak diminishes. The CCIs are more favored at higher uranium concentrations. However, the intensity of the 992 nm peak decreases steadily with increasing temperature suggesting the exothermic nature of the complexation process. The thermodynamic data and reported structural studies indicate the formation of an inner-sphere complex under the conditions of this study. In addition, the spectral changes also suggest the formation of Np(iv) even in the presence of uranium at elevated temperatures. Solvent extraction studies using 1.1 M TBP and 1.1 M DHOA solutions in n-dodecane show that NpO2+–UO22+ complexes are extractable leaving NpO2+ in the aqueous phase.