In the present work, a convenient and straightforward approach to the preparation of borylated amidines based on the closo-dodecaborate anion [B₁₂H₁₁NCCH₃NHR]−, R=H, Alk, Ar was developed. This method has two stages. A nitrile derivative of the general form [B₁₂H₁₁NCCH₃]⁻ was obtained, using a modified technique, in the first stage. On the second stage the resulting molecular system interacted with primary amines to form the target amidine products. This approach is characterised by a simple chemical apparatus, mild conditions and high yields of the final products. The mechanism of the addition of amine to the nitrile derivative of the closo-dodecaborate anion was studied, using quantum-chemical methods. The interaction between NH₃ and [B₁₂H₁₁NCCH₃]⁻ ammonia was chosen as an example. It was found that the structure of the transition state determines the stereo-selectivity of the process. A study of the biological properties of borylated amidine sodium salts indicated that the substances had low toxicity and could accumulate in cancer cells in significant amounts.

The novel members of the 1,2-diboraoxazoles family have been obtained. In the present work, we have carried out the intramolecular ring-closure reaction of borylated iminols of general type [B₁₀H₉N=C(OH)R]⁻ (R = Me, Et, ⁿPr, ⁱPr, ^tBu, Ph, 4-Cl-Ph). This process is conducted in mild conditions with 83–87% yields. The solid-state structures of two salts of 1,2-diboraoxazoles were additionally investigated by X-ray crystallography. In addition, the phenomena of bonding interactions in the 1,2-diboraoxazole cycles have been theoretically studied by the Quantum Theory of Atoms in Molecules analysis. Several local and integral topological properties of the electron density involved in these interactions have been computed.

The preparation of novel nitrilium derivatives of closo-dodecaborate anion [B₁₂H₁₁NCR]⁻, R = n-C₃H₇, i-C₃H₇, 4-C₆H₄CH₃, 1-C₁₀H₇ is described. Target compounds were obtained in good yields (up to 73%). The synthesis of target borylated nitrilium derivatives was characterised by the simplicity of the chemical apparatus and the absence of the necessity for the purification of desired compounds. The crystal structures of previously obtained [B₁₂H₁₁NCCH₃]⁻ and novel [B₁₂H₁₁NCC₃H₇]⁻ were established with the help of X-ray structure analysis. DFT-analysis of several nitrilium derivatives [B₁₂H₁₁NCR]⁻, R = CH₃, C₃H₇, 4-CH₃C₆H₄ was carried out. The main peculiarities of the C≡N bond of the exo-polyhedral substituent were revealed in terms of bond lengths, bond orders and atomic charges. The LUMO orbitals of the systems considered were examined for understanding of the electrophilic nature of the nitrilium derivatives of the closo-dodecaborate anion.

The process of protonation of [2,6-B₁₀H₈O₂CCH₃]⁻ was investigated both theoretically and experimentally. The most suitable conditions for protonation of the derivative [2,6-B₁₀H₈O₂CCH₃]⁻ were found. The process of protonation was carried out in the presence of an excess of trifluoromethanesulfonic acid CF₃SO₃H at room temperature in dichloromethane solution. The structure of the resulting complex [2,6-B₁₀H₈O₂CCH₃*H^fac]⁰ was established using NMR data and the results of DFT calculations. An additional proton atom H^fac was found to be localized on one of the facets that was opposite the boron atom in a substituted position, and which bonded mainly with one apical boron atom. The main descriptors of the B-H^fac bond were established theoretically using QTAIM and NBO approaches. In addition, the mechanism of [2,6-B₁₀H₈O₂CCH₃]⁻ protonation was investigated.

Although the most promising applications of ionogels require their contact with aqueous media, few data are available on the stability of ionogels upon exposure to water. In this paper, a simple, easy-to-setup and precise method is presented, which was developed based on the continuous conductivity measurements of an aqueous phase, to study the washout of imidazolium ionic liquids (IL) from various silica-based ionogels immersed in water. The accuracy of the method was verified using HPLC, its reproducibility was confirmed, and its systematic errors were estimated. The experimental data show the rapid and almost complete (>90% in 5 h) washout of the hydrophilic IL (1-butyl-3-methylimidazolium dicyanamide) from the TMOS-derived silica ionogel. To lower the rate and degree of washout, several approaches were analysed, including decreasing IL content in ionogels, using ionogels in a monolithic form instead of a powder, constructing ionogels by gelation of silica in an ionic liquid, ageing ionogels after sol–gel synthesis and constructing ionogels from both hydrophobic IL and hydrophobic silica. All these approaches inhibited IL washout; the lowest level of washout achieved was ~14% in 24 h. Insights into the ionogels’ structure and composition, using complementary methods (XRD, TGA, FTIR, SEM, NMR and nitrogen adsorption), revealed the washout mechanism, which was shown to be governed by three main processes: the diffusion of (1) IL and (2) water, and (3) IL dissolution in water. Washout was shown to follow pseudo-second-order kinetics, with the kinetic constants being in the range of 0.007–0.154 mol⁻¹·s⁻¹.

In this work, a series of boronated amidines based on the closo-dodecaborate anion and amino acids containing an amino group in the side chain of the general formula [B₁₂H₁₁NHC(NH(CH₂)_nCH(NH₃)COOH)CH₃], where n = 2, 3, 4, were synthesized. These derivatives contain conserved α-amino and α-carboxyl groups recognized by the binding centers of the large neutral amino acid transporter (LAT) system, which serves as a target for the clinically applied BNCT agent para-boronophenylalanine (BPA). The paper describes several approaches to synthesizing the target compounds, their acute toxicity studies, and tumor uptake studies in vivo in two tumor models. The promising compound [B₁₂H₁₁NHC(NH(CH₂)₂CH(NH₃)COOH)CH₃]*3H₂O demonstrates low toxicity (LD₅₀ in a range from 150 to 300 mg/kg) and excellent solubility and also shows selective uptake in experimental melanoma in laboratory mice (T/N ratio remained >3 up to 60 min post-injection, with a maximum T/N of 6.2 ± 2.8 at 45 min).