Modification of cobalt bis(dicarbollide) ions with nitrile groups on carbon atoms: a unique low-temperature skeletal rearrangement due to the specific electron-donor character of CN substitution.

Herein, we report on the synthesis and stereochemistry of mono- and isomeric dinitrile derivatives of [(1,2-CBH)-3,3'-Co] ions. The shape and electronic properties of CN groups can apparently surmount the strain associated with the substitution of two vicinal carbon positions. Owing to electron donation to the cage, this results in a substituent-induced rearrangement of one of the carbon atoms to the upper pentagonal ring.

Preparation, Structure, Reactivity, Lewis Acidic and Fluorescence Properties of Arylpyridine Based Boron C,N-Chelates Featuring Weakly Coordinating Anions.

Herein, we present the preparation of a series of electronically and/or sterically distinct borenium-type species based on a simple 2-arylpyridine scaffold. Corresponding arylpyridine was firstly subjected to electrophilic borylation (BBr/i-PrNEt) and formed BBr chelate was reduced with LiAlH to yield arylpyridine boron dihydride. Elimination of one hydride led to Lewis acidic borenium-like products.

Novel Copper (II) Complexes with Fluorine-Containing Reduced Schiff Base Ligands Showing Marked Cytotoxicity in the HepG2 Cancer Cell Line.

Several novel copper (II) complexes of reduced Schiff bases containing fluoride substituents were prepared and structurally characterized by single-crystal X-ray diffraction. The complexes exhibited diverse structures, with the central atom in distorted tetrahedral geometry. The biological effects of the products were evaluated, specifically their cytotoxicity, antimicrobial, and antiurease activities, as well as affinity for albumin (BSA) and DNA (ct-DNA).

Vanadium-Containing Ionic Liquids Derived from Complexes of Modified Edta as Catalysts of Epoxy-Anhydride Ring-Opening Copolymerization.

A new type of vanadium-containing ionic liquids (ILs) was synthesized by cation exchange from barium salts of oxidovanadium(IV) complexes stabilized by edta and its congeners (dcta, oedta, and heedta) serving as pentadentate ligands. All starting barium salts and several magnesium and cesium salts, serving as models for the cation exchange, were structurally characterized by single-crystal XRD analysis. The synthesized ILs consisting of organic cations (BuN, Bmim, and BuP) and complex anions ([VO(edta)], [VO(dcta)], [VO(oedta)], and [VO(heedta)]) were characterized by analytical and spectroscopic methods including EPR spectroscopy and cyclic voltammetry.

Correction: Synthetic routes to carbon substituted cobalt bis(dicarbollide) alkyl halides and aromatic amines along with closely related irregular pathways.

Correction for 'Synthetic routes to carbon substituted cobalt bis(dicarbollide) alkyl halides and aromatic amines along with closely related irregular pathways' by Jan Nekvinda , , 2024, , 5816-5826, https://doi.org/10.1039/D4DT00072B.

Synthetic Chameleon Turns into Oximes, Nitrones, and Hydroxylamines when Exposed to Blue Light.

A metal-free, user-friendly photochemical transformation of nitroalkanes to oximes, nitrones, and hydroxylamines has been developed. The visible-light-induced reactions are catalyzed by the readily available photoredox organocatalyst 4CzIPN and use inexpensive amines as reductants. Broad in scope and tolerant of multiple functional groups and heterocycles, the transformation proceeds under mild conditions.

Synthetic routes to carbon substituted cobalt bis(dicarbollide) alkyl halides and aromatic amines along with closely related irregular pathways.

Carbon substituted cobalt bis(dicarbollide) alkyl halides [(1-X-(CH)-1,2-CBH)(1,2-CBH)-3,3'-Co]MeN (X = Br, I; = 1-3) are prepared in high yields (>90%) from their corresponding alcohols without side skeletal substitutions. These species offer access to the synthesis of aromatic cobalt bis(dicarbollide) amines, however only for particular terminal halogen substitution, the propylene pendant arm, and under appropriately controlled reaction conditions. Thus, the compounds substituted at cage carbon atoms with a propylene linker and terminal aromatic amine groups could be prepared.

Expanding Luminescence Horizons in Macropolyhedral Heteroboranes.

Luminescence is observed in three novel macropolyhedral nineteen- and eighteen-vertex chalcogenaboranes: SeBH (1), SeBH (3) and SeBH (4). This led us to the recognition that previously published macropolyhedral heteroborane species might also exhibit luminescence. Thus, the known nineteen- and eighteen-vertex dithiaboranes SBH (2), n-SBH (5) and i-SBH (6) were synthesised and also found to exhibit a range of luminescent properties.

Chemistry of Carbon-Substituted Derivatives of Cobalt Bis(dicarbollide)(1) Ion and Recent Progress in Boron Substitution.

The cobalt bis(dicarbollide)(1) anion (), [(1,2-CBH)-3,3'-Co(III)](1), plays an increasingly important role in material science and medicine due to its high chemical stability, 3D shape, aromaticity, diamagnetic character, ability to penetrate cells, and low cytotoxicity. A key factor enabling the incorporation of this ion into larger organic molecules, biomolecules, and materials, as well as its capacity for "tuning" interactions with therapeutic targets, is the availability of synthetic routes that enable easy modifications with a wide selection of functional groups. Regarding the modification of the dicarbollide cage, syntheses leading to substitutions on boron atoms are better established.

Antimicrobially Active Zn(II) Complexes of Reduced Schiff Bases Derived from Cyclohexane-1,2-diamine and Fluorinated Benzaldehydes-Synthesis, Crystal Structure and Bioactivity.

A series of Schiff base ligands obtained by the condensation of -cyclohexane-1,2-diamine and fluorinated benzaldehydes were prepared, followed by their reduction with NaBH. The reduced ligands were employed in the synthesis of zinc complexes of the general formula [ZnCl(L)]. The structures of both the original and the reduced Schiff bases, as well as of the zinc complexes, were characterized by single-crystal X-ray analysis, along with NMR and IR spectroscopy.

Stabilization of propene molybdenum and tungsten half-sandwich complexes by intramolecular coordination of a thioether function.

This study reports the stabilizing effect of an intramolecularly coordinated thioether function in propene complexes of the general formula [{η:κ-CH(CH)SR}M(CO)(η-CHMe)][BF] (M = Mo, W; R = Et, Ph). They are formed by protonation of allyl analogues [{η-CH(CH)SR}M(CO)(η-CH)] by tetrafluoroboric acid in non-coordinating solvents. In contrast to analogues with unsubstituted Cp ligands, these propene complexes are isolable in a pure form and characterized by NMR spectroscopy.

Bipyridine Ruthenium(II) Complexes with Halogen-Substituted Salicylates: Synthesis, Crystal Structure, and Biological Activity.

Ruthenium complexes currently represent a perspective subject of investigation in terms of potential anticancer therapeutics. Eight novel octahedral ruthenium(II) complexes are the subject of this article. Complexes contain 2,2'-bipyridine molecules and salicylates as ligands, differing in position and type of halogen substituent.

A Window into the Workings of -BH Luminescence-Blue-Fluorescent Isomeric Pair 3,3'-Cl-BH and 3,4'-Cl-BH (and Others).

The action of AlCl on room-temperature tetrachloromethane solutions of -BH () results in a mixture of fluorescent isomers, 3,3'-Cl-BH () and 3,4'-Cl-BH (), together isolated in a 76% yield. Compounds and are capable of the stable emission of blue light under UV-excitation. In addition, small amounts of other dichlorinated isomers, 4,4'-Cl-BH (), 3,1'-Cl-BH (), and 7,3'-Cl-BH () were isolated, along with blue-fluorescent monochlorinated derivatives, 3-Cl-BH () and 4-Cl-BH (), and trichlorinated species 3,4,3'-Cl-BH () and 3,4,4'-Cl-BH ().

Macropolyhedral Chalcogenaboranes: Insertion of Selenium into the Isomers of BH.

High yields of novel macropolyhedral selenaboranes are reported. Reactions of the monoanions of the - and -isomers of BH with powdered selenium in THF variously give new macropolyhedral selenaboranes: 19-vertex [SeBH] anion , 19-vertex [SeBH] anion , 20-vertex [SeBH] anion , and 19-vertex [SeBH] anion . Single-cluster [-SeBH] anion and neutral -SeBH also result.

Interaction of Adenosine, Modified Using Carborane Clusters, with Ovarian Cancer Cells: A New Anticancer Approach against Chemoresistance.

Platinum compounds remain the first-line drugs for the treatment of most lethal gynecological malignancies and ovarian cancers. Acquired platinum resistance remains a major challenge in gynecological oncology. Considering the unique physicochemical properties of the metallacarboranes modifier and the significant role of nucleoside derivatives as anticancer antimetabolites, we designed and synthesized a set of adenosine conjugates with metallacarboranes containing iron, cobalt, or chromium as semi-abiotic compounds that influence the cisplatin sensitivity of ovarian cancer cells.

Low-dimensional compounds containing bioactive ligands. Part XIV: High selective antiproliferative activity of tris(5-chloro-8-quinolinolato)gallium(III) complex against human cancer cell lines.

Four gallium(III) complexes, [Ga(ClQ)]⋅MeOH (1 - MeOH), [Ga(ClQ)] (1), [Ga(BrQ)] (2), [Ga(dIQ)] (3) and [Ga(CQ)] (4), were prepared (H-ClQ = 5-chloro-8-quinolinol, H-BrQ = 7-bromo-8-quinolinol, H-dIQ = 5,7-diiodo-8-quinolinol, H-CQ = 5-chloro-7-iodo-8-quinolinol) and characterised by elemental analysis, IR and NMR spectroscopy. Single crystal structure analysis of 1 - MeOH confirmed that the complex has a molecular structure with gallium(III) metal ion coordinated in mer-fashion by N- and O-donor atoms of three ClQ ligands. Stability of all complexes in DMSO was proved by H NMR spectroscopy.