A new synthetic method for obtaining [RhCl(cod)(NHC)] complexes (1–4) (cod = η⁴-1,5-cyclooctadiene, NHC = N-heterocyclic carbene: IMes, SIMes, IPr, and SIPr, respectively) is reported together with the catalytic properties of 1–4 in nitrile hydration. In addition to the characterization of 1–4 in solution by ¹³C NMR spectroscopy, the structures of complexes 3, and 4 have been established also in the solid state with single-crystal X-ray diffraction analysis. The Rh(I)-NHC complexes displayed excellent catalytic activity in hydration of aromatic nitriles (up to TOF = 276 h⁻¹) in water/2-propanol (1/1 v/v) mixtures in air.

The special C–C bond in icosahedral closo-dicarbadodecaboranes and its high plasticity have been highlighted several times, which is reflected in the ease of tuning the C–C bond distance with different substituents. Apart from this special case, the other bonds within the carborane clusters have not been investigated yet. DFT calculations demonstrated that the elongation of C–B and B–B bonds is ruled by the same effects as the well-investigated C–C bond; however, stretching of B–B generally requires more energy. These results indicate that the bonds of the carborane clusters do not differ significantly; in fact, they possess similar properties. The computational results encouraged us to synthesize the most promising derivatives. The distinct tuning was achieved by the variation of π-donor substituents. In the case of the 9,10-m-carboranyl-disulfanide derivatives, the B9–B10 bond distance is elongated up to 1.92(2) Å.

Mixing weak acids and bases can produce highly complicated binary mixtures, called pseudo‐protic ionic liquids, in which a complex network of effects determines the physicochemical properties that are currently impossible to predict. In this joint computational‐experimental study, we investigated 1‐methylimidazole‐acetic acid mixtures through the whole concentration range. Effects of the varying ionization and excess of either components on the properties, such as density, diffusion coefficients, and overall hydrogen bonding structure were uncovered. A special emphasis was put on understanding the multiple factors that govern the conductivity of the system. In the presence of an excess of acetic acid, the 1‐methylimidazolium acetate ion pairs dissociate more efficiently, resulting in a higher concentration of independently moving, conducting ions. However, the conductivity measurements showed that higher concentrations of acetic acid improve the conductivity beyond this effect, suggesting in addition to standard dilution effects the occurrence of Grotthuss diffusion in high acid‐to‐base ratios. The results here will potentially help designing novel electrolytes and proton conducting systems, which can be exploited in a variety of applications.

Water-soluble salan ligands were synthesized by hydrogenation and subsequent sulfonation of salens (N,N’-bis(slicylidene)ethylenediamine and analogues) with various bridging units (linkers) connecting the nitrogen atoms. Pd (II) complexes were obtained in reactions of sulfosalans and [PdCl₄]²⁻. Characterization of the ligands and complexes included extensive X-ray diffraction studies, too. The Pd (II) complexes proved highly active catalysts of the Suzuki–Miyaura reaction of aryl halides and arylboronic acid derivatives at 80 °C in water and air. A comparative study of the Pd (II)–sulfosalan catalysts showed that the catalytic activity largely increased with increasing linker length and with increasing steric congestion around the N donor atoms of the ligands; the highest specific activity was 40,000 (mol substrate) (mol catalyst × h)⁻¹. The substrate scope was explored with the use of the two most active catalysts, containing 1,4-butylene and 1,2-diphenylethylene linkers, respectively.