A novel stibacarbaborane cluster with adjacent antimony atoms exhibiting unique pnictogen bond formation that dominates its crystal packing

We have prepared nido-7,8,9,11-Sb2C2B7H9, the first cluster with simultaneous Sb-B, Sb-C and Sb-Sb atom pairs with interatomic separations with magnitudes that approach the respective sums of covalent radii. However, the length of the Sb-Sb separation in this cluster is slightly less than the sum of the covalent radii. Quantum chemical analysis has revealed that the crystal packing of nido-7,8,9,11-Sb2C2B7H9 is predominantly dictated by pnictogen (Pn) bonding, an unconventional σ-hole interaction. Indeed, the interaction energy of a very strong Sb2⋯H-B Pn-bond in the nido-7,8,9,11-Sb2C2B7H9 dimer exceeds -6.0 kcal mol-1. This is a very large value and is comparable to the strengths of known Pn-bonds in Cl3Pn⋯π complexes (Pn = As, Sb)

Organization of the patient income on internal surgery

Management příjmu pacienta na interní ambulanci je soubor postupně na sebe navazujících úkonů, jehož hlavní součástí je spolupráce pacienta a zdravotnického personálu. Hlavním úkolem mé bakalářské práce bylo zjistit akceptaci čekací doby na ošetření, vliv psychického stavu a rodinného příslušníka při čekání na výsledky vyšetření. Součástí šetření bylo odhalení negativních vlivů a emocí, které vnímají pacienti během čekání na výsledky vyšetření s následnou možností hospitalizace. V praktické části jsem se zaměřila na dotazníkové šetření. Ze tří předpokladů byly dva potvrzeny.Katedra ošetřovatelství a porodní asistenceObhájenoThe management of patient's admission at an internal ambulatory is a cluster of operations linking to each other, requiring a cooperation between patients and medical staff. The major aim of my bachelor's thesis was to find out an acceptance of treatment latency, an effect of dependent's presence and actual mental condition during waiting for results of examination. All at once, I investigated all the negative effects and emotions related to the waiting for the results and potencial admission to a hospital. In the practical part of my bachelor's thesis, I focused on the questionnaire survey especially. Out of three assumptions, two were verified

Hydrolýza vanadocen dichloridu

A key hydrolysis product of vanadocene dichloride was isolated and structurally characterized. The oligomeric character of the species precludes its detection by classical EPR spectroscopic tools. A detailed study of the with high purity reagents disproves appearance of Cp2V(OH)2, which was postulated previously based on mechanistic approach.Klíčový produkt hydrolýzy vanadocendichloridu byl izolován a strukturně charakterizován. Oligomerní charakter této částice neumožňuje její detekci pomocí EPR spektroskopie. Podrobná studie vyloučila možnost vzniku dríve postulovaného komplexu Cp2V(OH)2

Unikátní reaktivita alfa-ketiminopyridinového ligandu s alkyl-kovy: Syntéza a ROP epsilon-kaprolaktonu

The reaction of an alpha-ketimininopyridine ligand 2-((Me)C = N(C6H3-2,6-iPr(2)))-6-(OMe)C5H3N (L-1) with metal-alkyls, such as MeLi, Et2Zn, Me3Al and Me2AlCl, was studied. The reaction of L-1 with MeLi led exclusively to the formation of [2-((H2C)C-N(C6H3-2,6-iPr(2)))-6-(OMe)C5H3N]Li center dot(THF)(2) (1 center dot(THF)(2)) with a deprotonated ketimine methyl group as a product of methane elimination. The treatment of L-1 with Et2Zn provided, at the first stage, only complex [2-((Me)C = N(C6H3-2,6-iPr(2)))-6-(OMe)C5H3N]ZnEt2 (2). The nonstability of 2 led to ethane elimination along with the deprotonation of a ketimine methyl group, which further yielded [2-((H2C)C-N(C6H3-2,6-iPr(2)))-6-(OMe)C5H3N]ZnEt (3). In contrast, Me3Al reacted with L-1 in a carboalumination fashion and [2-((Me)(2)C-N(C6H3-2,6-iPr(2)))-6-(OMe)C5H3N]AlMe2 (4) was isolated. In the case of Me2AlCl, an ionic species {[2-((Me)C = N(C6H3-2,6-iPr(2)))-6-(OMe)C5H3N]AlMe2}(+) {Me2AlCl2}(-) (5) was formed as a result of a spontaneous dissociation of Me2AlCl initiated by the ligand L-1. Since compounds 2-5 contain a metal-alkyl fragment, they were used as pre-catalysts in ROP of epsilon-caprolactone, as well as compound 1 center dot(THF)(2).Alfa-ketimininopyridinový ligand 2-((Me)C=N(C6H3-2,6-iPr2))-6-(OMe)C5H3N (L1) byl studován v reakcích s alkyl-kovy, jako jsou MeLi, Et2Zn, Me3Al a Me2AlCl. Reakce ligandu L1 s MeLi vedla výhradně ke vzniku [2-((H2C)CN(C6H3-2,6-iPr2))-6-(OMe)C5H3N]Li·(THF)2 (1·(THF)2) s deprotonovanou methylovou skupinou ketiminu jako produktu eliminace metanu. Reakce ligandu L1 s Et2Zn poskytla v prvním stupni pouze komplex [2-((Me)C=N(C6H3-2,6-iPr2))-6-(OMe)C5H3N]ZnEt2 (2). Nestabilita sloučeniny 2 vedla k eliminaci etanu společně s deprotonací methylové skupiny ketiminu za poskytnutí [2-((H2C)CN(C6H3-2,6-iPr2))-6-(OMe)C5H3N]ZnEt (3). Naproti tomu, Me3Al reagoval s ligandem L1 karbaluminačním způsobem a byl izolován amid hlinitý [2-((Me)2C-N(C6H3-2,6-iPr2))-6-(OMe)C5H3N]AlMe2 (4). V případě reakce s Me2AlCl vznikl iontový komplex {[2-((Me)C=N(C6H3-2,6-iPr2))-6-(OMe)C5H3N]AlMe2}+{Me2AlCl2}-(5) jako produkt spontánní disociace Me2AlCl iniciované ligandem L1. Vzhledem k faktu, že sloučeniny 2-5 obsahují alkyl-kovový fragment, byly tyto sloučeniny použity jako katalyzátory v ROP -kaprolaktonu, stejně jako sloučenina 1·(THF)2

An intramolecular C–N cross-coupling of β-enaminones: a simple and efficient way to precursors of some alkaloids of Galipea officinalis

2-Aroylmethylidene-1,2,3,4-tetrahydroquinolines with the appropriate substituents can be suitable precursors for the synthesis of alkaloids from Galipea officinalis (cuspareine, galipeine, galipinine, angustureine). However, only two, rather low-yielding procedures for their synthesis are described in the literature. We have developed a simple and efficient protocol for an intramolecular, palladium or copper-catalysed amination of both chloro- and bromo-substituted 3-amino-1,5-diphenylpent-2-en-1-ones leading to the above-mentioned tetrahydroquinoline moiety. The methodology is superior to the methods published to date

Komplexy molybdenu s polymethylthiomethylboraty.

Organometallic molybdenum compounds bearing poly[(methylthio)methyllborates, [(eta(3)-C3H5)Mo (CO)(2)(kappa(3)-PhTt)] and [Bu4N][{((eta(3)-C3H5)Mo(CO)(2)Cl)(2)(kappa(2):kappa(2)-RTt)], where PhTt = phenyltris[(methylthio) methyllborate and RTt = tetralds[(methylthio)methyl]borate, have been obtained by ligand exchange reaction from [(eta(3)-C3H5)Mo(CO)(2)(NCMe)(2)Cl] and appropriate borate. The PhTt ligand provides tridentate face-capping coordination to the central metal while the RTt acts as a bridging ligand and connects two [(eta(3)-C3H5)Mo(CO)(2)Cl] monomeric units by unusual kappa(2):kappa(2)-coordination mode. Both compounds were fully characterized by spectroscopic methods and X-ray crystallography.Organokovové sloučeniny nesoucí polymethylthioboraty byly připraveny a charakterizovány dostupnými spektroskopickými metodami. Struktura dvou produktů byla stanovena rentgenovou difrakční analýzou

Nové deriváty substituovaných 6-fluorbenzthiazolových diamidů: syntéza, antifungální aktivita a cytotoxicita

A new series of 1-[(1R)-1-(6-fluoro-1,3-benzothiazol-2-yl) ethyl]-3-substituted phenyl diamides were synthesized in vitro as potential antifungal agents. Chemical structures of the synthesised compounds were substantiated by IR, H-1, C-13, F-19 nuclear magnetic resonance spectra, high resolution mass spectrometry, elemental analysis and also by X-ray diffraction. In addition, the cytotoxicity of the most active compounds was investigated against cancer cell line (Jurkat) and one type of normal lung fibroblast cells (MRC-5) by (2,3-bis-(2-methoxy4-nitro-5-sulfophenyl)-2H-tetrazolium-5-carboxanilide) tetrazolium salt reduction assay, propidium iodide flow cytometry assay and xCELLigence system allowing a label-free assessment of the cells proliferation. Compounds indicated as 11e, 11g, 11j, 11n and 11o, were the best of the series, showing minimum inhibitory concentration values of 6.25-50 mu g/mL against pathogenic strains Candida albicans HE 169, Candida tropicalis 31/HK and Candida parapsilosis p69. Moreover compounds 11e, 11g, 11j and 11o did not show any cytotoxic effect against human Jurkat and MRC-5 cells.Byla syntetizována nová řada 1 - [(lR) -l- (6-fluor-l, 3-benzothiazol-2-yl) ethyl] -3-substituovaných fenyl diamidů a testována in vitro jako potenciální antifungální činidla. Chemické struktury syntetizovaných sloučenin byly charakterizovány IR, H-1, C-13, F-19 NMR spektry, hmotnostní spektrometrií s vysokým rozlišením, elementární analýzou a také rentgenovou difrakcí. Kromě toho byla zkoumána cytotoxicita nejaktivnějších sloučenin proti rakovinové buněčné linii (Jurkat) a jednomu typu normálních plicních fibroblastových buněk (MRC-5) pomocí (2,3-bis- (2-methoxy4nitro-5- ) -2H-tetrazolium-5-karboxanilidu) testu redukce tetrazoliové soli, testu průtokové cytometrie a systému xCELLigence umožňujícím bezzásahové vyhodnocení proliferace buněk. Sloučeniny označené jako 11e, 11g, 11j, 11n a 11o byly nejlepší ze série, vykazující MIC hodnoty 6,25-50 ug / ml proti patogenním kmenům Candida albicans HE 169, Candida tropicalis 31 / HK a Candida parapsilosis p69 . Navíc sloučeniny 11e, 11g, 11j a 11o nevykazovaly žádný cytotoxický účinek proti buňkám, linií JURKAT a MRC-5

Titanocene(III) pseudohalides: an ESR and structural study

A series of complexes of the type [Ti(′Cp)2Y] {′Cp = η5-C5H5 (Cp), η5-C5H4SiMe3 (SiCp), η5-1,3-C5H3(Me3Si)2 (Si2Cp); Y = Cl−, CN−, NCS−, NCSe−, dicyanamide (dca), tricyanomethanide (tcm) and 1,2,3,4-thiatriazol-5-thiolate (ttt)} were prepared and studied by ESR spectroscopy. Ring-substituted compounds [Ti(SiCp)2Cl], [Ti(Si2Cp)2Cl], [Ti(SiCp)2CN] and [Ti(Si2Cp)2CN] dissolved in coordinating solvents exist in an equilibrium with solvated species. The thiatriazolthiolate ligand in complexes [Ti(′Cp)2(ttt)] behaves as a S,N-chelator to yield a thermally unstable 4-membered chelate ring having the ESR signal with significant splitting due to coupling with one 14N nucleus. Solutions of [Ti(′Cp)2Y] (Y = NCS−, NCSe−, dca and tcm) readily dissolve the additional pseudohalide salt giving anionic species [Ti(′Cp)2Y2]− with a characteristic ESR pattern caused by super-hyperfine splitting by two 14N nuclei. Cyanide complexes dissolve additional KCN as well, but no coupling to ligand nuclei (neither 14N nor 13C) was observed. The frozen-solution ESR spectra of [Ti(Si2Cp)2Cl], [Ti(Si2Cp)2CN] and [Ti(′Cp)2Y] (Y = NCS−, NCSe− and ttt) are typical for monomeric species of rhombic symmetry. The remaining complexes form dimeric {[Ti(Cp)2Cl]2, [Ti(SiCp)2Cl]2, [Ti(′Cp)2dca]2, and [Ti(′Cp)2tcm]2} or trimeric {[Ti(SiCp)2CN]3} adducts under these conditions. The nuclearity of [Ti(Cp)2CN] cannot be accurately determined by ESR spectroscopy due to its poor solubility but the presence of species with a higher spin ground state was confirmed (similar to the case of the above-mentioned dimers and trimer) by the observation of formally forbidden half-field transition. The reported results of the crystal structure analysis of [Ti(SiCp)2Cl], [Ti(Cp)2tcm], [Ti(SiCp)2tcm], [Ti(SiCp)2dca], [Ti(SiCp)2CN], and [TiCp2(NCS)]2O corroborate the findings based on spectroscopic measurements

Ferrocenový donor připojený k pyridinovému nebo pyridiniovému akceptoru prostřednictvím systematicky se prodlužujícího pi-konjugovaného řetězce

Nine chromophores with ferrocene donor and pyridine/pyridinium acceptors have been prepared and further investigated. The performed X-ray analysis showed partially polarized and geometrically oblate pyridine unit. An extension of the pi-system and N-quaternization were revealed as suitable tools for exclusive manipulation of the LUMO with the almost steady HOMO. Whereas the electrochemical HOMO-LUMO gap can be tuned from 3.01 to 1.49 eV, the high- and low-energy absorption bands were found within the range of 280-402/456-547 nm. The pyridinium chromophores showed distinct negative solvatochromism. A thorough DFT analysis has been performed; it turned out that ferrocene donor is capable of two principal D-A interactions, whose employment depends on the appended electron-withdrawing moiety.Bylo připraveno a zkoumáno devět chromoforů s ferrocenovým donorem a pyridinovými nebo pyridiniovými akceptory. Provedené X-ray analýzy potvrzují částečně polarizovanou a planární pyridinovou jednotku. Rozšíření pi-konjugovaného systému a N-kvarternizace vedou k posunu LUMO s téměř ustáleným HOMO. Elektrochemický rozdíl HOMO-LUMO se mění v rozmezí od 3.01 do 1.49 eV a vysoko- a nízkoenergetické absorpční pásy byly pozorovány v rozmezí 280-402 resp. 456-547 nm

Železnatý komplex s modifikovaným bispidinovým ligandem: Příprava a katalytické zasychání alkydů.

Modified iron(II) bispidine complex was synthesized and characterized by analytical methods including crystal structure determination on single crystal. Catalytic activity of the title compound toward autoxidation process was established on alkyd resin of long oil length. The standardized mechanical tests as well as kinetic studies, performed on thin layers of alkyd coatings, revealed high activity at considerably lower concentrations than usual for commercial cobalt(II) 2-ethylhexanoate. Due to high solubility in non-polar solvents, title compound is applicable without necessity of pre-dissolution in a polar organic solvent as in case of parent [Fe(bispi)Cl]Cl.Železnatý komplex s modifikovaným bispidinovým ligandem byl připraven a charakterizován analytickými metodami, které zahrnovaly RTG analýzu na monokrystalu. Katalytická aktivita tohoto komplexu byla studována na alkydu dlouhé olejové délky