European Journal of Inorganic Chemistry

Pure aqua complexes are frequent for the 3d but scarce for the 4d and 5d transition-element series. Since water can conveniently be substituted, aqua complexes facilitate biomedical applications. Thismicroreview discusses complexes of the manganese triad containing water ligands. A particular focus is placed on technetium and its organometallic aqua ion [⁹⁹Tc(OH₂)₃(CO)₃]⁺.

Oxidovanadium complexes are known to consume alkylating toxins and yield alcohols. These reactions may help in thedevelopment of second-generation cancer prevention compounds.

A rare pentanuclear bismuth(III) zwitterionic thiolate complex, [Bi₅(Tab)₁₈](PF₆)₇(NO₃)₈·6MeCN [1; Tab = 4-(trimethylammonio)benzenethiolato], was obtained from the reaction of Bi(NO₃)₃ with TabHPF₆ in a 1:4 molar ratio in MeCN/MeOH in the presence of Et₃N.

On the basis of X-ray crystal structures of monomeric, (–)-sparteine-coordinated lithiosilanes, the influence of the steric demand of the substituents at silicon on their molecular structures was studied. NMR spectroscopic studies indicated equivalent structures in solution and in the solid state. DFT calculations provided very small energy differences between the diastereomers.

Two ruthenium(II) complexes were synthesised by using a linear back-to-back bridging ligand based on a dipyrazolylpyridine coordination unit. The structural, electrochemical and spectroscopic properties show that this new bridging ligand can be considered as structural and electronic alternative to the widely used terpyridine-based bridging ligand systems.

Two new cyclophanes differing only in the aromatic ring substitution have been prepared. Potentiometric measurements suggest the m-substituted ligand is tetradentate in the CuL²⁺ complex whereas the p-cyclophane is tridentate. DFT calculations suggest this change in the coordination mode is not principally related to first coordination sphere effects but to changes in the hydrogen bond network.

Reaction of (COT)LnI(thf)₃ with Li[N(SiHMe₂)₂] yields (COT)dilanthanide sandwich complexes featuring distinct heterobridged core moieties Ln(μ-I)_n[μ-N(SiHMe₂)₂]_mLn (Ln = La: n = 1, m = 2; Ln = Nd, Sm: n = 2, m = 1). Utilization of K[N(SiHMe₂)₂] affords a (COT)monolanthanide silylamide complex.

Iron-containing nanospheres were obtained from self-assembly of an amphiphilic siderophore derived from 8-hydroxyquinoline. Cryogenic transmission electronmicroscopy images revealed evolution from micelles to flecked spherical structures with time.

Heterocyclic or cage-like compounds are formed by the double deprotonation of the hydrazine derivatives H₅C₆–(H)N–N(H)–C₆H₅ and H₂N–NC₄H₄ with AlH₃·NMe₂Et. 1-Aminopyrrole gave a novel structural motif, in which five Al–H fragments are bridged by five dianionic hydrazinediido ligands.

In the hydroformylation of 1,1-diphenylethene, a high activation barrier was found for the branched alkyl-Rh(CO)₃ intermediate, but not for the linear intermediate. The path leading to the branched aldehyde is thus abandoned early. CO addition, instead of CO migratory insertion or H₂ oxidative addition and aldehyde reductive elimination, was found to be the critical step.

Diphenylboryl complexes of 2,6-bis(pyrazolyl)anilines are more robust and more highly-emissive colour-tuneable fluorophores than derivatives with only one pyrazolyl bound to the aniline ring. Evident from VT-NMR studies, the origin of these favourable characteristics is likely kinetic via promotion of chelate ring formation should dissociation occur.

The rhodium(II) complexes [Rh₂(μ-OOCCH₃)₂(Me₂bpy)₂(H₂O)₂]²⁺ were chemically and electrochemically reduced to the Rh^1.5+ wire {[Rh₂(μ-OOCCH₃)₂ (Me₂bpy)₂]⁺}_n(BF₄)_n with infinite Rh–Rhbonds. The molecular wire shows strong antiferromagnetic properties. Redox properties of the wires prepared chemically and electrochemically are similar.

The set of DOTA-like complexes lacking a directly coordinated water molecule is studied to explore the relationship between the second hydration sphere and MRI-relevant parameters, and the influence of the ligand pendant arms (size, hydrophilicity) on the complex properties is discussed.

The cleavage of bis(1,2,3-thiadiazole)s provides a new family of bis(alkynethiolate)gold(I) derivatives [Au₂(S–C≡C–spacer–C≡C–S)L₂] (L = PR₃ or C₆F₅). X-ray studies confirm the dinuclear structure for (PPN)₂[Au₂(S–C≡C–C≡C–S)(C₆F₅)₂] and [Au₂{3,5-(S–C≡C)₂–C₇H₇N}(PPh₃)₂] {PPN = bis(triphenylphosphane)iminium}.

A series of interesting coordination polymers with V-shaped 4,4′-oxybis(benzoic acid) have been prepared. The crystal structures and topological analysis of these compounds, along with a systematic investigation of the effect of metal ions and neutral ligands on their ultimate frameworks, will be discussed.

A [1+1] asymmetric compartmental macrocycle, bearing a –CH₂C₆H₄OH pendant arm, and related mononuclear, Ln₂ homodinuclear and LnLn′ heterodinuclear complexes are reported. Their properties in thesolid-state and in different coordinating solvents have been investigated. The final decomposition at 1200 °C of the heterodinuclear complexes gives pure LnLn′O₃ oxides.

Hierarchical butterfly-like CuO architectures composed of oriented attached rhombic nanoplatelets were synthesized by a simple hydrothermal method. The mechanism for the formation of the CuO hierarchical architectures is proposed.