European Journal of Inorganic Chemistry

Ambiphilic and amphoteric molecules, which have both a donor and an acceptor group, have great potential in many applications. This microreview will focus on the coordination chemistry of a subclass of these molecules, in which the donor groups can be represented as L_n ligands. The various strategies to overcome aggregation and the reactivity and properties of these complexes will be discussed.

Novel imido clusters of Nd³⁺ involving four or six metal centres and with a cubane or rhombododecahedron core structure were obtained from the reaction of NdI₃ and {[PhNMg(thf)]₆} in thf or pyridine. Similar reaction with UI₃(py)₄ led to a tetranuclear U^IV derivative.

First examples of the coordination chemistry of the As₄S₃ cage are reported. Compounds (As₄S₃)(CuCl)_n, which form in interdiffusion experiments of solutions of As₄S₃·M(CO)₅ in CH₂Cl₂ and CuCl_n in CH₃CN (n = 1) or CH₃OH (n = 2),represent first examples of the novel S-only coordination mode of the intact E₄S₃ cage molecules (E = P, As).

A hexanuclear metallamacrocycle was synthesized by using N-acetylaminobenzhydrazide and a manganese ion. The metal–organic framework based on a hexanuclearmetallamacrocycle as a supramolecular building block is quite different from those obtained from similar ligands.

Metastable Sr_0.5TaO₃ was prepared byusing layer-structured H₂Sr_1.5Ta₃O₁₀ by direct dehydration and nanosheet processing.Nanosheet processing can provide a possible route for the synthesis of materials with novel disordered structures.

Highly uniform twofold-shaped CeO₂ dendrites were prepared by using an approach that involves the thermal decomposition of the precursor. Precursors (average size 10 μm) were prepared from Ce(NH₄)₂(NO₃)₆ and CO(NH₂)₂ in a H₂O/diethanolamine solution. DEA plays an important role in the formation of the products. The dendritic pattern of the precursor is almost retained in the CeO₂ product.

H₂ elimination from guanidine–boranes: Several reaction pathways have to be considered in the thermal and catalytic dehydrogenation of guanidine–boranes.

Thermal reactions of (Me₂C)(Me₂Si)[(η⁵-C₅H₃)Mo(CO)₃]₂ (1) with a series of phosphanylalkynes PhnP(C≡CR)_3–n were reported. P–C(alkyne) bond cleavage andphosphanylalkyne rearrangement products were obtained, in addition to the complexes in which the phosphanylalkynes acted as disubstituted acetylenes.

Functional analogues for hemes and phytofluors, a Mn corrole and a bis(bodipy) carrying two adjacent propionate substituents, are available in two steps from a simple bipyrrolic precursor. Hydrolysis of the ester groups to the free acid is successful for the corrole and yields buffer-soluble material, while for the dinuclear bis(bodipy), hydrolysis of B–F bonds is observed.

A near-infrared luminescent macroporous material and a near-infrared luminescent/magnetic bifunctional macroporous material, which may offer the opportunity to develop new materials suitable for optical amplifiers, were synthesized by using polystyrene microspheres and Fe₃O₄@polystyrene core–shell nanoparticles, respectively, as templates.

The sandwich-type heteroleptic tetrapyrrole cerium complex Ce₂(dap)₂(pc) was synthesized from [Ce(acac)₃]·nH₂O, Li₂pc, and metal-free D₂h-type diazaporphyrin. The molecular structure indicated an unexpected asymmetrical disposition of the ligands, with two adjacent dap moieties and one outer pc ring.

One-dimensional chain derivatives of the general formula [M(acac)₂(μ-bipyridine)] were obtained from (acetylacetonato)cobalt(II) or (trifluoromethylacetylacetonato)copper(II) derivatives and bipyridine-like bridging ligands. Magnetic susceptibility studies show weak antiferromagnetic interactions along the chain.

The synthesis, solution properties and reactivity of novel alkylaluminium complexes bearing a modified phenoxyimine ligand containing a pendant imidazolium moiety are reported. Investigation of solution structures by NMR spectroscopy revealed the involvement of the coordinated ligand in hydrogen bonding with halide anions.

Reactions between [Ru(PPh₃)₃Cl₂] and biacetylmonoxime acetyl-/aroylhydrazones (H₂L) provide ruthenium(III) complexes trans-[Ru(^tL)(PPh₃)Cl₂], where ^tL^– represents the N,N,O-donor transformed ligand. In this unique metal-assisted chemical transformation of H₂L, the –CH₃ group at the oxime end becomes =CHPHPh₃.