Theoretical Insight into B–C Chemical Bonding in <i>Closo</i>-Borate [B_nH_n−1CH₃]²⁻ (n = 6, 10, 12) and Monocarborane [CB_nH_nCH₃]⁻ (n = 5, 9, 11) Anions

A theoretical investigation of mono-methyl derivatives of closo-borate anions of the general form [BnHnCH3]2– (n = 6, 10, 12) and monocarboranes [HCBnHnCH3]− (n = 5, 9, 11) was carried out. An analysis of the main bonding descriptors of exo-polyhedral B–C bonds was performed using the QTAIM (quantum theory of “Atoms in Molecules”), ELF (electron localisation function), NBOs (natural bond orbitals) analyses and several other approaches for the estimation of B–C bond orders (viz. Laplacian bond order (LBO), fuzzy bond order (FBO) and Mayer and Wiberg formalisms). Based on the data obtained on electron density descriptors, it can be concluded that orbital interaction increases with increasing boron cluster size. The present investigation provides a better understanding of exo-polyhedral B–C bond phenomena in boron cluster systems. The data obtained can be used to estimate B–C bond strength, which can be useful for studies devoted to the synthesis and properties of boron cluster systems

New Aspects of the Synthesis of <i>closo</i>-Dodecaborate Nitrilium Derivatives [B₁₂H₁₁NCR]⁻ (R = <i>n</i>-C₃H₇, <i>i</i>-C₃H₇, 4-C₆H₄CH₃, 1-C₁₀H₇): Experimental and Theoretical Studies

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

Primary Amine Nucleophilic Addition to Nitrilium <i>Closo</i>-Dodecaborate [B₁₂H₁₁NCCH₃]⁻: A Simple and Effective Route to the New BNCT Drug Design

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

Synthesis of Disubstituted Carboxonium Derivatives of <i>Closo</i>-Decaborate Anion [2,6-B₁₀H₈O₂CC₆H₅]⁻: Theoretical and Experimental Study

A comprehensive study focused on the preparation of disubstituted carboxonium derivatives of closo-decaborate anion [2,6-B10H8O2CC6H5]− was carried out. The proposed synthesis of the target product was based on the interaction between the anion [B10H11]− and benzoic acid C6H5COOH. It was shown that the formation of this product proceeds stepwise through the formation of a mono-substituted product [B10H9OC(OH)C6H5]−. In addition, an alternative one-step approach for obtaining the target derivative is postulated. The structure of tetrabutylammonium salts of carboxonium derivative ((C4H9)4N)[2,6-B10H8O2CC6H5] was established with the help of X-ray structure analysis. The reaction pathway for the formation of [2,6-B10H8O2CC6H5]− was investigated with the help of density functional theory (DFT) calculations. This process has an electrophile induced nucleophilic substitution (EINS) mechanism, and intermediate anionic species play a key role. Such intermediates have a structure in which one boron atom coordinates two hydrogen atoms. The regioselectivity for the process of formation for the 2,6-isomer was also proved by theoretical calculations. Generally, in the experimental part, the simple and available approach for producing disubstituted carboxonium derivative was introduced, and the mechanism of this process was investigated with the help of theoretical calculations. The proposed approach can be applicable for the preparation of a wide range of disubstituted derivatives of closo-borate anions

Protonation of Borylated Carboxonium Derivative [2,6-B10H8O2CCH3]&minus;: Theoretical and Experimental Investigation

The process of protonation of [2,6-B10H8O2CCH3]&minus; was investigated both theoretically and experimentally. The most suitable conditions for protonation of the derivative [2,6-B10H8O2CCH3]&minus; 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*Hfac]0 was established using NMR data and the results of DFT calculations. An additional proton atom Hfac 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-Hfac bond were established theoretically using QTAIM and NBO approaches. In addition, the mechanism of [2,6-B10H8O2CCH3]&minus; protonation was investigated

Fused 1,2-Diboraoxazoles Based on closo-Decaborate Anion–Novel Members of Diboroheterocycle Class

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]&minus; (R = Me, Et, nPr, iPr, tBu, Ph, 4-Cl-Ph). This process is conducted in mild conditions with 83&ndash;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