Two series of new diorganotin complexes 1-10, with abiraterone acetate and abiraterone, were synthesized and characterized using 1H, 13C, 119Sn NMR, IR spectroscopy, ESI-MS, and elemental analysis. The anti-inflammatory activity of compounds was evaluated by their inhibition ability toward lipoxygenase. The most active compounds were dibutyltin complexes 4 and 9. Antiproliferative activity in vitro was studied on HCT-116, MCF-7, and PC-3 cancer cell lines, as well as on primary rat skin fibroblasts. Compounds with dibutyltin and diphenyltin moieties (4, 9 and 5, 10, respectively) demonstrated the highest antiproliferative effect, significantly inducing apoptosis in HCT-116 and PC-3 cells and causing the cell cycle arrest at the G2/M phase. These complexes also exhibited significant antibacterial activity comparable to that of ciprofloxacin against the Bacillus subtilis strain. Complex 5 showed antifungal activity against Candida albicans, although it was weaker than metronidazole.

A series of novel organotin(IV) complexes 1–5, incorporating diclofenac and a polydentate chelating ligand system, were synthesized and comprehensively characterized by NMR (1H, 13C, 119Sn), IR spectroscopy, single-crystal XRD, and elemental analysis. The compounds were evaluated for their bioactive potential. They demonstrated mild antioxidant activity in radical scavenging (DPPH, NBT) and reducing power (CUPRAC) assays, with the tert-butyl derivative 4 showing consistently notable results. The complexes also exhibited lipoxygenase (LOX) inhibitory activity. A key feature is their increased stability across different pH values, attributed to the robust chelating framework. Furthermore, the complexes display strong luminescence with an emission maximum at 470 nm and exhibit photocontrolled cytotoxicity. The combination of bioactivity, pH stability, luminescent properties, and light-activated toxicity positions these multifunctional Sn(IV) complexes as promising candidates for further development as theranostic and photodynamic therapy agents.

In this work, a series of novel germylenes, RN(CH2CH2NR')2Ge R ' = Ph, R = Et (1); R ' = Ph, R = Bn (2); R ' = Ph, R = t-Bu (3); R ' = R = Ph (4); R ' = Bn, R = Et (5); R ' = Bn, R = Bn (6); R ' = Et, R = Et (7); R ' = Et, R = Bn (8), based on 1,4,7-triazaheptanes have been obtained. The compositions and structures of the novel compounds were established by elemental analysis and 1H and 13C NMR in the solid state by X-ray diffraction analysis (1-4), and it has been shown that germylenes are monomeric. The redox properties of compounds 1-4 and previously obtained germylene 10 (R ' = C6F5, R = Bn) in acetonitrile were studied by cyclic voltammetry (CV), and their optoelectronic properties were studied by UV-vis absorption spectroscopy. The easily oxidizing properties of the presented germylenes have been determined. An analysis of frontier molecular orbitals was carried out for compounds 1-8, 10 (R ' = C6F5, R = Bn), 11 (R ' = C6F5, R = Me), and Lappert's germylene, Ge[N(SiMe3)2]2. It has been established that the nature of the substituents on the nitrogen atoms covalently bonded to the germanium atom has a significant effect on the energy of the frontier molecular orbitals.

New pyridinyl SN-bi- (1) 1 ) and SNS-tridentate (3) 3 ) ligands were obtained by hydrothiolation of substituted alkenes with thioacetic acid. A number of these, as well as the known SN- (2) 2 ) and SNO-- (4, 4, 5 ) ligands were used in the synthesis of methylaluminum complexes. Molecular structure of the monoligand, [2,6-MePy(CH2CMe2S)]AlMe2 2 CMe 2 S)]AlMe 2 (1a), 1a ), [2,6-MePy(CH2CH2CMe2S)]AlMe2 2 CH 2 CMe 2 S)]AlMe 2 (2a), 2a ), [2,6-Py(CH2CMe2S)2AlMe] 2 CMe 2 S) 2 AlMe] (3a) 3a ) and [2,6-Py(CH2CH2CMe2SH) 2 CH 2 CMe 2 SH) (CH2CH2CMe2O)AlMe2]2 2 CH 2 CMe 2 O)AlMe 2 ] 2 (5a), 5a ), and the diligand, [2,6-MePy(CH2CMe2S)]2AlMe 2 CMe 2 S)] 2 AlMe (1b), 1b ), complexes were studied in solution (NMR spectroscopy) and in crystal (1a, 1a , XRD); the dependence between the ligand and the complex structure formed was established. The catalytic activity of 1-3a, 5a and 1b in the ring-opening polymerization of epsilon-caprolactone was studied in bulk, indicating high control of the process.

A series of substituted bis(triazole) derivatives of organodigermanes (1-3) containing reactive phenolic and sugar functional groups, [1,4-C2HN3(R)GePh2-](2) (R = beta-(d)-glucopyranoso-C5H5O(OAc)(3)CH2OAc (1); R = CH2-1,2,3,5-(HO)C6H2(t-Bu)(2) (2); and R = CH2-1,2,3,5-(HO)C6H2(CHO)(t-Bu) (3)), was synthesized by the copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction. The structural features (1, XRD analysis) and optical properties (1-3, absorbance, and emission) of these digermanium heterocyclic compounds were studied. The antioxidant (DPPH test), lipoxygenase inhibitory (inhibition of LOX 1-B), and antiproliferative activities (MTT test; HCT-116, MCF-7, A-549 cancer cell lines) of differently substituted 1-6 (R = p-BrC6H4CH2 (4); R = CH2COOEt (5); R = CH2CH2O-p-C6H4CHO (6)) were investigated, indicating their promising antioxidant (for 2 EC50 103 +/- 4 mu M) and lipoxygenase inhibition activity (for 4 IC50 29 +/- 2 mu M), moderate antiproliferative activities (for 5 IC50 55-71 mu M), and low toxic properties (WI-38, IC50 > 36 mu M). Comparison of the biological activity of the leader digermanes 2, 4, and 5 with related organic triazoles 1,4-C2HN3(R) (2a, 4a, 5a) and monogermanes 1,4-C2HN3(R)GePh3 (2b, 4b, and 5b) indicates the influence of the Ge-Ge fragment.

Synthesis of two types of complexes (heteroleptic vs homoleptic) is accomplished by an elegant variation of the ligand design. Heteroleptic ethyl zinc complexes 1a-3a were cleanly obtained via ethane elimination. Nevertheless, in the reaction of proligands 3 and 4 with Zn[N(SiMe3)2]2 performed at room temperature, only homoleptic complexes 3b and 4b can be isolated. Surprisingly, proligand 2 was found to cleanly produce amide heteroleptic zinc complex 2c in the reaction with Zn[N(SiMe3)2]2, and 2c seems to be the most promising in ringopening polymerization (ROP) among tested initiators in terms of activity.

The aim of this work was to understand the main structural features and ways of formation of Ge-O bonds in organogermanium compounds under the conditions of ArnGeHal4-n (Hal = halide) hydrolysis. The structural types of these compounds were considered, providing 11 blocks (A–K). The molecular structures of the novel compounds [(p-FC6H4)3Ge]2O (1), [(p-F3CC6H4)3Ge]2O (2), and cyclo-[(p-F3CC6H4)2GeO]4 (3) were studied through XRD (X-ray diffraction) analysis. The molecular structure of [(p-F3CC6H4)3GeO]4Ge (4), representing a novel structural type, was also investigated. The data presented in this study will be important in the design of materials with useful properties based on group 14 element derivatives with element–oxygen bonding.

Using the [3+2] cycloaddition reaction of [HC≡C-GePh2 -]2 (1) and a number of RCH2 N3 , this work described the synthesis of a series of novel heterocyclic digermanes, bitriazoles [1,4-C2 HN3 (CH2 R)GePh2 -]2 , 2-12 (R=Ph, p-Tol, p-C6 H4 NMe2 , p-C6 H4 OMe, p-C6 H4 Br, m-C6 H4 NO2 , 2-Naphth, CH2 -p-OC6 H4 CHO, CH2 -p-OC6 H4 COOMe, CH2 P(O)(OEt)2 , COOEt), difficult to produce by other methods. The structural peculiarities of these compounds were studied in detail by NMR spectroscopy and by XRD analysis (for 6, 9 and 10). The properties of 1-12 were studied by UV/vis and luminescence emission spectroscopy, electrochemistry and DFT calculations, indicating an effective conjugation in their molecules.

A highly efficient one-step approach to the macromonomer synthesis using modified aluminum complexes as catalysts of ring-opening polymerization (ROP) of ε-caprolactone and D,L-lactide was developed. The syntheses, structures, and catalytic activities of a wide range of aluminum salen complexes, 3a-c, functionalized with unsaturated alcohol (HO(CH2)4OCH=CH2) are reported. X-Ray diffraction studies revealed a tetragonal pyramidal structure for 3c. Among the complexes 3a-c, the highest activity in bulk ROP of ε-caprolactone and D,L-lactide was displayed by 3b, affording polyesters with controlled molecular weights at low monomer to initiator ratios (Mn up to 15,000 g mol−1), relatively high polydispersities (Ð~1.8) and high number-average functionalities (Fn up to 85%).

Due to the ever-increasing demand for healthy and safe food, much attention has been gained by natural food colorants. This study showed the culture fluid extract of the fungus Aspergillus cavernicola VKM F-906 to contain red pigment and monasnicotinic acid (MNA) in predominant amounts. The structure of the pigment corresponded to cis-cavernamine (red pigment, RP). Two tautomers, NH and OH forms, in rapid equilibrium were present in a solution of RP. The critical factors for RP to form were the presence of NH4+ salt and pH 6.3-6.5. In vitro experiments showed that MNA was synthesized from RP as a result of chemical transformations without the participation of enzymes. In this case, the main influence on the reaction rate is exerted by the pH of the medium, which is associated with the keto-enol tautomerism of RP in solution. The culture broth extract and MNA exhibited antifungal activity against Fusarium fungi.

A series of methyl and chlorido aluminum complexes decorated with diamidoamine ligands with different number of carbon atoms in the alkyl chains were prepared via methane elimination, salt methatesis route, transmetallation strategy or chlorination. They were investigated by various methods including F-19, Al-27 NMR spectroscopy and showed to be active catalysts of ring-opening polymerization of epsilon-Cl and L-La.

Metalcyclopentadienyl complexes (MCp)+ (M = Fe, Ru, Os) bound to the large polyaromatic hydrogenated hydrocarbon (PAH) C96H24 used as a model for pristine graphene have been studied using a density functional theory (DFT) generalized gradient approximation (PBE functional) to reveal their structural features and dynamic behavior. The inter-ring haptotropic rearrangements (IRHRs) for these complexes were shown to occur via two transition states and one intermediate. The energy barriers of the η6 ⇌ η6 IRHRs of the (MCp)+ unit were found to be 30, 27, and 29 kcal/mol for M = Fe, Ru, and Os, respectively. These values are significantly lower than the values found previously for smaller PAHs. Both polar and nonpolar solvents were found not to affect significantly the energy barrier heights. Investigated transition metal complexes could be used in general as catalysts in the design of novel derivatives or materials with promising properties. Metalcyclopentadienyl complexes (MCp)+ of PAHs show catalytic properties mainly due to their structural details as well as their important characteristic of inter-ring haptotropic rearrangement. IRHRs take place usually by intramolecular mechanisms. During IRHRs, the MLn organometallic groups (OMGs) undergo shifting along the PAH plane and could coordinate additional reagents, which is important for catalysis. Large PAHs such as graphene, fullerenes, and nanotubes possess intrinsic anticancer activity, and numerous arene complexes of Ru and Os have been proven to have anticancer properties as well. We suppose that coordinating Ru or Os to very large PAHs could synergistically increase the anticancer activity of resulting complexes.

Inter-ring haptotropic rearrangements (IRHRs) of different types are well-known phenomena in organometallic and catalytic chemistry. So far, they are reported for transition metal complexes with carbo- and heterocyclic polyaromatic hydrocarbons (PAH) of small and medium size. Here, we report DFT studies of RuCp+ shifts between neighboring six-membered rings (η6⇌ η6-IRHR) on an extra-large PAH as a model for graphene and compare it to naphthalene. Our calculations predict that η6⇌ η6-IRHRs proceed with much lower activation energy barrier of rearrangement in the case of the RuCp+ complex of η6-graphene model.

Two new austalide meroterpenoids, named austalides V and W (1 and 2), were isolated from the fungus Aspergillus ustus VKM F-4692. Their structures were elucidated by extensive spectroscopic analysis and by comparison with related known compounds. The main structural feature of both compounds is a tetrahydrofuranyl ring (G), a structural fragment, first found in austalides. Austalides V (1) and W (2) were able to inhibit the propagation of prostate and bladder cancer cells; this biologic activity is possibly related to the inhibition of a number of key pathways regulating cell growth and migration.

Interaction of organolithium reagent (η6-C6H5Li)Cr(CO)3 (1-Li) with ClSiMe2SiMe2Cl (2) resulted in [(OC)3Cr(η6-C6H5)]SiMe2SiMe2[(η6-C6H5)Cr(CO)3] (3), Me2Si[(η6-C6H5)Cr(CO)3]2 (4) and [(OC)3Cr(η6-C6H5)][SiMe2]4[(η6-C6H5)Cr(CO)3] (5); compounds 3 and 4 were isolated in preparative yields and fully characterized (multinuclear NMR, IR, UV/vis spectroscopy, mass spectrometry). The thermodynamics of this interaction was studied by DFT calculations, indicating several possible ways of synthesis of unexpected 4 and 5, which are obtained under rupture and formation of new SiSi bonds. The molecular structure of 3 was studied by single crystal XRD analysis.

The structural peculiarities (C1-C6 distances, bending of the ligand, conformation of organometallic group relative to the ligand, etc.), the isomerism and the mechanisms of inter-ring haptotropic rear-rangements (IRHR) in Cr(CO)(3) and CoCp complexes of 1,6-methano[10]annulene were investigated by DFT. An activation barrier of 28.0 kcal/mol, lower than that corresponding to naphthalene, was computed for the eta(6), eta(6)-IRHR in the mononuclear chromium complex. In the case of the mononuclear cobalt species, activations barrier of 33.8 and 31.3 kcal/mol were computed for the eta(4), eta(4)-IRHR in the trans and cis isomers, respectively. (C) 2017 Elsevier B.V. All rights reserved.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

The new aluminum compounds 1–3 modified by unsaturated alcohol, Me3−nAl(O(CH2)4OCHCH2)n (n = 1 (1), 2 (2), 3 (3)), are synthesized and investigated by multinuclear (1H, 13C, 27Al) NMR spectroscopy. The compounds 1–3 initiate living ring-opening polymerization of ε-caprolactone in bulk at 40–80 °C to afford polyesters with controlled molecular weight (Mn up to 35 000 g mol−1) and relatively narrow molecular weight distribution (Mw/Mn < 1.8). Among initiators studied here, aluminum trialkoxide shows the highest activity, whereas aluminum dialkoxide is a less active. In all cases, the fragment of unsaturated alcohol is transferred to the end of the polymeric chain with high degree of functionality (>85%) yielding macromonomers. These macromonomers are copolymerized with maleic anhydride to give poly(vinyl ether-co-maleic anhydride)-g-poly(ε-caprolactone) graft copolymers.