European Journal of Inorganic Chemistry

The cover picture shows a model structure of the human copper chaperone Atox1 bound to cisplatin (magenta: Pt; green: Cl; blue: N; white: H; yellow: S) and poses an intriguing question: Is platinum exchanged between transporters as it happens for copper? This major question is still lacking an answer. Details are presented in the Microreview by F. Arnesano, M. Losacco, and G. Natile on p. 2701 ff. For more on the story behind the cover research, see the Cover Profile. In the background is “the near-touching hands”, a detail of the Creation of Adam by Michelangelo.

An Updated View of Cisplatin Transport

The most exciting aspect of Bioinorganic Chemistry is the deep involvement of different areas of expertise, spanning from basic inorganic chemistry to life sciences, complemented by the use of the most advanced spectroscopic techniques such as in-cell NMR spectroscopy...

This and more about the story behind the cover in the Cover Profile and about the research itself on p. 2701 ff.

Membrane transporters and soluble chaperones of copper ions mediate cellular uptake of and resistance to platinum-based drugs. In this microreview, the interactions of cisplatin with the methionine-rich motifs of the copper permease Ctr1 and with the cysteine motifs of the cytosolic copper chaperone Atox1 are described. Only in the latter case does the drug retain its ammine ligands essential for antitumor activity.

The missing puzzle piece: [Au(η²-C₂H₄)₃]⁺[Al{OC(CF₃)₃}₄]^– in a spoke-wheel structure is the missing puzzle piece in the series of homoleptic univalent group 11 ethene complexes with the weakly coordinating anion [Al{OC(CF₃)₃}₄]^–. Herein, we describe the synthesis, characterization, and theoretical investigations of the second isolable, homoleptic η²-bound tris(ethene)gold(I) complex.

The reactivity of the drug auranofin, a gold(I) complex with anticancer properties, towards selenols and thiols is investigated by multinuclear NMR spectroscopy and DFT calculations. Useful insights that are relevant to the mechanism of inhibition of thioredoxin reductase are obtained.

[Cp*₂M₂O₅]-catalyzed (Cp* = pentamethylcyclopentadienyl) cyclooctene epoxidation is more efficient for M = Mo when the oxidant is tert-butyl hydroperoxide (TBHP)/decane, whereas it is more efficient for M = W when using H₂O₂/H₂O. Water has a negative effect with both oxidants, and H₂O₂ is a better oxidant than TBHP for both metals, but the relative effects are system-specific.

A thorough analysis of the chemical bonding patterns in two polymorphs of a cobalt(II) benzoate complex with substituted pyrazole ligands by using Bader's “Atoms in Molecules” theory reveals the crucial role of N–H···O hydrogen bonds in the stabilization of unfavorable [4+1] cobalt polyhedron.

Spin crossover and photomagnetic properties of iron(II) coordination polymers: In a series of three 1D complexes, the thermal spin-crossover properties were measured and the stabilities of the photoinduced high-spin states were probed through determination of the T(LIESST) values associated with the light-induced excited spin-state trapping (LIESST) effect.

Ionized supramolecular aggregates held together by chalcogen–nitrogen secondary bonding interactions (SBIs) are detected by mass spectrometry.

The new compounds K[Co(Hpydtz)(pydtz)], K[Ni(Hpydtz)(pydtz)], [Cu(pydtz)(EtOH)]_n and Na₂[Zn(pydtz)₂] [pydtz = pyridine-2,6-di(5-tetrazolate)] are characterised by single-crystal XRD, electron paramagnetic resonance (EPR) spectroscopy, magnetic measurements and UV/Vis absorption spectroscopy to assess the strength of the tridentate pydtz^2– ligand.

Two methods for the encapsulation of a Mn^IIIsalen complex in NaY zeolite lead to different modes of coordination at the metal. Cyclic voltammetry of the neat and heterogeneous complexes shows different electrochemical behaviour. The heterogeneous catalysts lead to similar or higher alkene conversion than the homogeneous catalyst. DFT confirmed distortion of the complex in a confined space.

The reaction of LSitBu [L = PhC(NtBu)₂] (1) with 4,4′-bis(dimethylamino)thiobenzophenone resulted in the [1+2]-cycloaddition product silathiacyclopropane 3, bearing a three-membered SiCS ring. The reaction of LSiC(SiMe₃)₃ (2) with 3,5-di-tert-butyl-o-benzoquinone leads to the [1+4]-cycloaddition product 4.

The mixed donor N-heterocyclic carbene/sulfur ligands CS^R (R = Me, Bn) coordinate to rhodium centres to provide complexes of the type [Rh(CS^R)(cod)]PF₆. The complexes were prepared by using the corresponding imidazolium salt precursors [HCS^R]PF₆. The complexes have been fully characterized by spectroscopic and analytical methods in addition to X-ray crystallography.

6,9-(Me₂S)₂-arachno-B₁₀H₁₂ reacts smoothly with ferrocenyl alkynes bearing simple and functional substituents at the triple bond to afford the respective 1-ferrocenyl-1,2-dicarba-closo-dodecaboranes in good yields. The compounds were structurally characterized by spectroscopic methods, X-ray crystallography, and voltammetric techniques.

The reaction of a Lewis base with a silylborane is central to a series of Lewis base-mediated reactions of silylboranes. For [K(18-C-6)OtBu] and an NHC the reaction products were isolated and characterized. Either the activation of a B–Si bond or the formation of Lewis acid/base adducts is observed. The reactivity of the reaction products toward selected electrophiles is studied.

Heterobimetallic rare earth–alkali metal binaphtholates (REMBs) are exquisite catalysts for asymmetric synthesis. No REMBs with fewer than three binaphtholates have yet been characterized in the solid state. We report the first X-ray structure analyses of REMBs with only two, and even one, chiral ligands.

Surface-functionalized carbon nanotubes (CNTs) with 100 % organic coverage exhibit parallel-aligned arrays with a tube distance of 26 nm in the absence of other templates. The alignment depends on the nature of the hydrophobic interaction between near-neighbor tubes. The depth of the perpendicular coating of the polysiloxane quaternary ammonium compound on the CNT surface is ca. 3.2 nm (inset).

Centimeter-sized Ba₂LaFeNb₄O₁₅ (BLFNO) crystals are obtained by a flux method. A frequency-dependent dielectric permittivity maximum is found (T_m = 100 K at 5 kHz), which indicates relaxor behavior. Single-crystal XRD analysis reveals an incommensurate structure at room temperature with a bidimensional modulation characterized by vectors q₁ = (α, α, 1/2) and q₂ = (α, –α, 1/2) with α = 0.295(1).