The tetranuclear complex H2Ru4(CO)11(µ4-η1,η5-CC5H4) (I) was obtained by the photochemical reaction of Ru3(CO)12 with Z-1-(4-tolyl)-3-phenylaminoprop-2-en-1-one (λ ≥ 210 nm). The structure of complex I was established by single crystal X-ray diffraction. According to X-ray diffraction data, the complex is described by a superposition of resonance structures, that is, the carbene cluster YCRu3, in which the substituent Y at the carbyne carbon atom is (η5-C5H4)Ru(CO)2, and a vinylidene complex containing a fulvene form of the ligand, in which the exocyclic carbenium carbon atom is additionally stabilized by coordination to a triangular ruthenium cluster. For description of the interatomic binding in I, quantum chemical calculations of the electronic structure of the molecule in the gas phase were carried out at the PBE0/def2TZVP level. The features of binding of the organic ligand to the metal core were described in terms of the atoms in molecules theory. According to the calculations, the C6H4 moiety in I is a fulvene type ligand in which two hydrogen atoms in the CH2 group have been replaced by ruthenium atoms.

The reactions of suspensions of the freshly prepared complexes [Ph2P(CH2)nPPh2] CoCl2 (n = 2 (dppeCoCl2), n = 3 (dpppCoCl2), n = 4 (dppbCoCl2); dppe is bis(diphenylphosphino)ethane, dppp is 1,3-bis(diphenylphosphino)propane, dppb is 1,4-bis-(diphenylphosphino)butane) with the salts [Na][R2C2B8H9] (R = H, Ph), which were obtained in situ by the treatment of carboranes 5,6-nido-R2C2B8H10 (R = H (1a), Ph (1b)) with NaH in THF at room temperature, afforded 18-electron cobaltahydridocarboranes with isonido structures, [1,1-{kappa 2-Ph2P(CH2)nPPh2}-1-H-isonido-1,2,4-CoR2C2B8H8] (R = H, n = 2 (2a), 3 (2b), 4 (2c); R = Ph, n = 2 (2d)). The treatment of nido-carborane 1a with potassium hydroxide followed by the addition of [Ph2P(CH2)nPPh2]CoCl2 (n = 2-4) in ethanol at 20 degrees C resulted in the formation of ethoxy-substituted complexes [1,1-{kappa 2-Ph2P(CH2)nPPh2}-1-H-3-(EtO)-isonido-1,2,4-CoC2B8H9] (3a-c, n = 2-4) apart from compounds 2a-c. All the newly prepared compounds were characterized by a combination of elemental analysis, multinuclear NMR spectroscopy, and IR spectroscopy. The structure of complex 2a was studied by X-ray diffraction analysis.

New tin(IV) complexes (Ln)SnR2 (R = n-Bu (I, II), t-Bu (III–V), and Ph (VI)) with O,N,O'-donor Schiff bases are synthesized. The molecular structures of compounds I and IV in the crystalline state are determined by XRD (CIF files CCDC nos. 2309864 (I) and 2309422 (IV)). The photophysical properties of the complexes are studied in comparison with the previously synthesized compounds containing phenyl or ethyl hydrocarbon groups at the tin atom. All compounds luminesce in chloroform: the emission bands are observed in the range from 580 to 638 nm. Both the groups at the tin atom and nature of the substituents in Schiff bases significantly affect the relative quantum yield. The anti/prooxidant activity of (Ln)SnR2 in the reactions with the ABTS (2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid)) radical cation and superoxide radical anion, in the oxidative DNA damage, and during lipid peroxidation in vitro is studied. A weak antibacterial activity against the bacterial strains Staphylococcus aureus ANCC 6538 and E. faecium ATCC 3576 are observed for some compounds. The in vitro antiproliferative properties for a number of the complexes are studied for the HTC-116 and А-549 cancer cell lines. The coordination of the organometallic fragment with the O,N,O'-tridentate ligands is found to induce a pronounced decrease in the cytotoxicity of the complexes.

The reactions of copper(ii) and zinc(ii) acetates with anions of 5-phenylfuran-2-carboxylic acid (Hphfur) and 5-nitro-1,10-phenanthroline (nphen) or 2,2′-bipyridine (2,2′-bpy) in the MeOH/MeCN system afforded mononuclear complexes of the composition [Cu(phfur)2(nphen)H2O] (1) and [Zn(phfur)2(2,2′-bpy)]•H2O (2). The structures of these complexes were determined by X-ray diffraction analysis (XRD). According to the XRD data, the copper atom in molecular complex 1 is in a distorted square-pyramidal environment (SQ(CuN2O3) = 0.68); the zinc atom in molecular complex 2, in a distorted trigonal-bipyramidal environment (SQ(ZnN2O3) = 3.87). The supramolecular level of 1 is mediated by intermolecular π–π interactions between the aromatic moieties of the ligands and represents a 3D supramolecular structure. in the structure of 2, the water molecules of crystallization are involved in intermolecular hydrogen bonds, resulting in the formation of centrosymmetric hydrogen-bonded dimers. The supramolecular level of 2 is mediated by C—H⋯O and C—H⋯π interactions. According to the simultaneous thermal analysis, complexes 1 and 2 are characterized by different types of thermal destruction. Thus, the explosophoric groups in the ligands of compound 1 are responsible for an intense exothermic effect. The results of biological assays show a certain correlation between the type of the substituted moiety in the heterocycle and the activity against the non-pathogenic Mycolicibacterium smegmatis strain.

The reactions of suspensions of the freshly prepared complexes [Ph2P(CH2)nPPh2] CoCl2 (n = 2 (dppeCoCl2), n = 3 (dpppCoCl2), n = 4 (dppbCoCl2); dppe is bis(diphenylphosphino)ethane, dppp is 1,3-bis(diphenylphosphino)propane, dppb is 1,4-bis-(diphenylphosphino)butane) with the salts [Na][R2C2B8H9] (R = H, Ph), which were obtained in situ by the treatment of carboranes 5,6-nido-R2C2B8H10 (R = H (1a), Ph (1b)) with NaH in THF at room temperature, afforded 18-electron cobaltahydridocarboranes with isonido structures, [1,1-κ2-Ph2P(CH2)nPPh2-1-H-isonido-1,2,4-CoR2C2B8H8] (R = H, n = 2 (2a), 3 (2b), 4 (2c); R = Ph, n = 2 (2d)). The treatment of nido-carborane 1a with potassium hydroxide followed by the addition of [Ph2P(CH2)nPPh2]CoCl2 (n = 2–4) in ethanol at 20 °C resulted in the formation of ethoxy-substituted complexes [1,1-κ2-Ph2P(CH2)nPPh2-1-H-3-(EtO)-isonido-1,2,4-CoC2B8H9] (3a–c, n = 2–4) apart from compounds 2a–c. All the newly prepared compounds were characterized by a combination of elemental analysis, multinuclear NMR spectroscopy, and IR spectroscopy. The structure of complex 2a was studied by X-ray diffraction analysis.

Взаимодействием ацетата бария(II) и 2-фуранкарбоновой кислоты (пирослизевая, Hfur) в водно-спиртовом растворе получен координационный полимер состава [Ba5(fur)10(H2O)4]n (1). По данным РСА 1 содержит три симметрически-независимых катиона Ba2+, различающиеся способами координации fur- анионов и координационными числами. Все три атома кислорода фуроат-анионов образуют хелатные и мостиковые координационные связи с катионами, приводящие к сложно устроенному 3D-каркасу с сотоподобной структурой. Сетка катионов Ba2+ в 1, представляющая чередующиеся би- и трехъядерные линейные фрагменты, обусловливает высокую термическую стабильность по данным синхронного термического анализа (СТА). Дегидратация координированных молекул воды из состава 1 не приводит к разрушению каркаса до 400 °С.

A coordination polymer with the [Ba 5 (fur) 10 (H 2 O) 4 ] n composition ( 1 ) is prepared by the reaction of barium(II) acetate and 2-furancarboxylic acid (pyrosmucus, Hfur) in an aqueous alcoholic solution. The XRD data show that 1 contains three symmetrically independent Ba 2+ cations with different coordinations of fur – anions and different coordination numbers. All three oxygen atoms of the furoate anions are connected by chelate and bridging coordination bonds with cations to form a complex honeycomb 3D framework. The simultaneous thermal analysis (STA) shows that high thermal stability of 1 is due to the network of Ba 2+ cations formed by alternating bi- and trinuclear linear fragments. Dehydration of coordinated water molecules from the composition of 1 does not cause the framework destruction up to 400 °C.

The reaction of copper(II) and zinc(II) acetates with 3-furancarboxylic (HFur) and 2-thiophenecarboxylic (HTph) acids with subsequent addition of 3,5-dimethylpyrazole (HDmpz) gave mononuclear complexes [M(L) 2 (HDmpz) 2 ] (M = Cu(II), L = Fur – ( I ), Tph – ( II ); Zn(II), L = Fur – ( III )). The structures of compounds I – III were determined by X-ray diffraction. According to X-ray diffraction data, I and II are isostructural: the central Cu(II) atom occurs in a square planar environment formed by two oxygen atoms of carboxylate anions and HDmpz nitrogen atoms; in III , the Zn atom is in the tetrahedral environment of two furoate anions and HDmpz molecules, thus forming the {MO 2 N 2 } groups. The complexes are additionally stabilized in the crystal by inter- ( I and II ) and intramolecular ( III ) hydrogen bonds. The biological activity of I – III was determined in relation to the non-pathogenic Mycolicibacterium smegmatis.

Reactions of molybdenum complexes with a η 3 -propargyl ligand with nucleophilic reagents (PPh 3 , PPh 2 H, Pr 2 i NH, Py) were studied. These reactions were found to give two types of products: 1) mono- or dicationic complexes with a 2-substituted allylic ligand (PPh 2 H, Pr 2 i NH, PPh 3 ); 2) complexes with a η 2 -ammonio(phosphonio)allene ligand (Py, PPh 3 ). The reactivity of molybdenum complexes was compared with that of Re, Pt, and Pd propargyl complexes, which revealed similarities and differences in their behavior depending on various factors. Molybdenum 1- and 2-phosphonioallyl complexes were obtained, the latter was studied by X-ray diffraction analysis.

Polymer complexes of the composition {[Cu 2 (fur) 4 (bpy)] n • n MeOH} ( 1 ) and {[Ag 3 (fur)(bpy) 4 ] n •2 n fur·13.5nH 2 O} ( 2 ) were synthesized by the reactions of copper(ii) and silver(i) acetates, respectively, with anions of furancarboxylic acid (Hfur) and 4,4’-bi-pyridine (bpy) under different synthesis conditions. The structures of the new complexes were established by X-ray diffraction (XRD) analysis. According to the XRD data, complex 1 is a polymer, in which the molecular metal oxide moieties are connected in a monodentate manner through bpy to form a 1D structural motif. The coordination environment of the copper(ii) atom in complex 1 can be described as a square pyramid {CuO 4 N}; the coordination number is 5. ionic complex 2 contains three nonequivalent Ag i atoms in different coordination environment with different coordination numbers of the complexing metal (CN Ag(1) = 4; CN Ag(2)Ag(3) = 2). The supramolecular level of complex 2 is a 3D structure stabilized by different types of interactions, such as hydrogen bonds, π-stacking and ar-gentophilic interactions. The simultaneous thermal analysis demonstrated that complex 1 undergoes desolvation and decarboxylation at temperatures below 234 °C, whereas the bipyridine moieties coordinated to the copper(ii) atoms are not completely eliminated even at 500 °C. The in vitro biological activity of complexes 1 and 2 was evaluated against the non-pathogenic mycobacterial strain Mycolicibacterium smegmatis .

Tetranuclear cluster [Ru(μ3-CO)Cp]4 (I) is synthesized as a minor product in the thermal reaction of cyclopentadiene with Ru3(CO)12 aimed at preparing ruthenium dimer [Ru(CO)2Cp]2. The spectral (13С and 1H NMR, IR) and structural studies are carried out for cluster I. Under different conditions, the crystallization of cluster I gives dark cherry-colored crystals of two types: cluster Ia and its tetrahydrate Ib. The structures of compounds Ia and Ib are determined by X-ray diffraction (XRD) (CIF files CCDC nos. 2241197 and 2241199, respectively). A comparative analysis of the cluster geometry shows that the distortion of the Ru4(CO)4 cage in compound I from the ideal Td symmetry in the structure of the pure compound is due to anisotropy of intermolecular contacts in the crystal. Specific features of chemical binding in the [Ru(μ3-CO)Cp]4 cluster and its iron-containing analog are studied by DFT calculations using topological analysis of the electron density comparing the energy characteristics and effective force constants of binding interactions. A necessity to use criteria of elastic deformations of interatomic interactions (force constants) for the correction description of such structural chemical phenomena as structural nonrigidity of the cage in transition metal clusters is demonstrated.

The reactions in the Cu(OAc)2⋅H2O–phytic acid–2,2'-bipyridine (bpy) system in aqueous methanol solutions resulted in the formation of a molecular different-ligand tetranuclear complex [(Cu4(bpy)4(PO4)2(CO3)(H2O)2]⋅13H2O (I), the structure of which was established from the X-ray diffraction data (CCDC no. 2262998). The molecule of complex I contains four non-equivalent Cu2+ cations, coordinating each two phosphate anions ( PO_4^3 - remaining after the transformation of the phytate ring), four neutral bpy molecules, two water molecules, and one carbonate anion ( CO_3^2 - ). The presence of a large number of solvate water molecules in the outer coordination sphere gives rise to a hydrogen-bonded framework involved in stabilization of the crystal packing. Study of the antimycobacterial activity of I against non-pathogenic Mycolicibacterium smegmatis strain revealed high biological efficacy.

Tetranuclear cluster [Ru(mu(3)-CO)Cp](4) (I) is synthesized as a minor product in the thermal reaction of cyclopentadiene with Ru-3(CO)(12) aimed at preparing ruthenium dimer [Ru(CO)(2)Cp](2). The spectral ((13)& Scy; and H-1 NMR, IR) and structural studies are carried out for cluster I. Under different conditions, the crystallization of cluster I gives dark cherry-colored crystals of two types: cluster Ia and its tetrahydrate Ib. The structures of compounds Ia and Ib are determined by X-ray diffraction (XRD) (CIF files CCDC nos. 2241197 and 2241199, respectively). A comparative analysis of the cluster geometry shows that the distortion of the Ru-4(CO)(4) cage in compound I from the ideal T-d symmetry in the structure of the pure compound is due to anisotropy of intermolecular contacts in the crystal. Specific features of chemical binding in the [Ru(mu(3)-CO)Cp](4) cluster and its iron-containing analog are studied by DFT calculations using topological analysis of the electron density comparing the energy characteristics and effective force constants of binding interactions. A necessity to use criteria of elastic deformations of interatomic interactions (force constants) for the correction description of such structural chemical phenomena as structural nonrigidity of the cage in transition metal clusters is demonstrated.

A series of mono- and polyfunctional carborane organosilicon derivatives were prepared with good yields based on the hydrosilylation reactions of allylcarboranes with hydride-containing organosilicon compounds such as tetramethyldisiloxane, decamethylpentasiloxane and triethoxysilane in the presence of Karstedt's catalyst.

Ferrocenylacetylene 1 protonates a superacidic polymer Nafion in sc-CO2 (35 ?, 9 MPa) to form the alpha-ferrocenylvinyl cation, FcC(+) = CH2 ( 2 , Fc = ferrocenyl). Carbocation 2 alkenylates in situ 1,3-dithiane or 1,3,5-trithiane (35 ?, 35 MPa) to give the mono and disulfonium salts with Nafion anion. An anion exchange in the last ones for tetrafluoroborate afforded the disulfonium salts 4 and 12 , whose deprotonation produced, after a sequence of transformations, the neutral unsaturated 8-membered heterocycles, 2-ferrocenyl-3,7-dithiacyclooct-1-ene 10 and 2-ferrocenyl-3,5,7-tritiacyclooct-1-ene 14 . Along with 14 , the reaction of 1 with 1,3,5-trithiane furnished two other neutral sulfur heterocycles, 2,4-diferrocenyl5-thiacyclohexa-1,3-diene 18 , and 1-ferrocenyl-3,5-dithiacyclohex-1-ene 23 . These transformations proceed at room temperature via the C-S bond scission followed by a formation of new C -C bond. Compounds 10, 14, 18, 23 were fully characterized by the NMR spectra. The molecular structures of 10, 14, 18, 23 were elucidated by X-ray study. (c) 2022 Published by Elsevier B.V.

Anovel facile way of synthesis of closo-ruthenacarboranes with chelate 1,2-bis(diphenylphosphino)ethane (dppe) with high yields was proposed. It was found that the interaction of the three-bridged 5,6,10-{Cl(Ph3P)2Ru}-[5,6,10-(μ-H)3-10-H-exo-nido-7,8-C2B9H10] (1) with dppe in acetonitrile or CH2Cl2/acetonitrile mixture leads to the formation of novel diamagnetic ruthenacarborane cluster 3-СNMe-3,3-[κ2-dppe]-closo-3,1,2-RuC2B9H11 (2) along with some amount of ionic compound [trans-(CH3CN)RuCl(dppe)2]+[C2B9H12]− (3) which may be also converted to 2 increasing its total yield. The reaction of 2 bearing divalent ruthenium with carbon tetrachloride or HCl gives the known 17-electron paramagnetic complex 3-Сl-3,3-[κ2-dppe]-closo-3,1,2-RuC2B9H11 (4)..The detailed investigation of the previously described method of synthesis of 4 from 3-H-3Cl-3,3-(PPh3)2-closo-3,1,2-RuC2B9H11 (5) allowed us to characterize the forming by-products as 3-PPh3-3,3,8-(Ph2P(CH2)2PPh-μ-(C6[H4-о)-closo-3,1,2-RuC2B9]H10 (6) and 3-[κ1-dppe]-3,3-[κ2-dppe]-closo-3,1,2-RuC2B9H11 (7). The obtained ruthenacarborane clusters undergo reversible Ru(II)/Ru(III) transition. It was shown that the complexes 2, 4 and 6 show good activity as catalysts for Atom Transfer Radical Polymerization of methyl methacrylate.

Crystals of glycinium dicitratoborate monohydrate H3NCH2COOH[B(C6H6O7)2] · Н2О have been synthesized and selected for the first time. Their structure is determined by X-ray diffraction analysis: triclinic system, sp. gr. Р$$\bar {1}$$, and Z = 2. The crystals consist of cation–anion layers, in which all structural units (dicitratoborate anion, glycinium cation, and crystallization-water molecule) are bound firmly by numerous hydrogen bonds.

The reactions of Cd(NO 3 ) 2 ∙ 4H 2 O and Eu(NO 3 ) 3 ∙ 6H 2 O with potassium salts of the benzoic acid derivatives and 2,2'-bipyridine (Bipy) in ethanol, under the same synthesis conditions, afford the homo- and heterometallic complexes: [Eu 2 Cd 2 (BA) 8 (NO 3 ) 2 (Bipy) 2 ] ( I , BA is benzoic acid anion), [Ln 2 Cd 2 (4-TBA) 10 (Bipy) 2 ] (Ln = Eu ( II ), Tb ( III ); 4-TBA is 4-(trifluoromethyl)benzoic acid anion), [Cd(4-CBA) 2 (H 2 O)(Bipy)] ( IV , 4-CBA is 4-cyanobenzoic acid anion), [Cd(PFBA) 2 (H 2 O)(Bipy)] n ( V , PFBA is pentafluorobenzoic acid anion), and [Cd 2 (4-APFBA) 4 (Bipy) 2 ] ∙ 4H 2 O ( VI , 4-ATFBA is 4-amino-2,3,5,6-tetrafluorobenzoic acid anion). The structures of new complexes I , II , IV , and VI are determined by X-ray structure analysis (CIF files CCDC nos. 1970348, 1970350, 1970347, and 1970351, respectively). The isostructural character of complexes II and III is confirmed by X-ray diffraction analysis. The structures and compositions of the series of isolated compounds I – VI are determined by the nature of substituents in the benzoate anion. The photoluminescence properties of compounds II and III are studied.