bluuebunny/crossref_metadata_2025 huggingface dataset:
Estudos Nacionais sobre as Assistências de Enfermagem e de Psicologia ao Idoso Residente em Instituição de Longa Permanência
Authors: Monteiro Andreane Nathalia Pereira de Almeida , Pereira Juliane Da Silva , Valença Mércia Alcântara Feitosa , Batista Maria Amanda Lima , Barbosa Luciclaudio Da Silva , Santos Silvana Cavalcanti dos , Alexandre Ana Carla Silva , Leite-Salgueiro Claudia Daniele Barros
Published: August 2018

Este é um estudo de revisão integrativa sobre a produção científica brasileira, englobando a práxis do enfermeiro e do psicólogo na assistência prestada à saúde do idoso residente em Instituição de Longa Permanência para Idosos, que expõe o perfil dos trabalhos publicados em âmbito nacional, no período de 2010 a 2015, indexados nas bases de dados: da Biblioteca Virtual de Saúde (BVS), SciELO, LILACS, Portal Capes e Google Acadêmico. Foram encontrados 47 trabalhos publicados em português. Vinte e sete artigos foram selecionados, sendo a maioria publicada em 2012, em periódicos de enfermagem e gerontologia. A amostra foi apresentada em um quadro com a distribuição dos artigos (n=27), com descrição de indicadores como ano de publicação, título, autor (es), modalidade, área de atuação e objetivos dos artigos selecionados. Os critérios de classificação dos artigos do presente estudo foram descritos por modalidade: artigo de revisão, estudos teóricos e publicação original. Verificou-se ampla discussão na literatura, especialmente com enfoque na assistência prestada pela enfermagem, ao idoso residente em ILPI. Entretanto, escassez de pesquisas nacionais evidenciando as duas atuações profissionais relacionadas na prestação de assistência ao público alvo em questão.
O Protagonismo do Enfermeiro na Política Nacional de Humanização do Parto e do Nascimento e com vistas a Erradicação de Abuso e Violência Obstétrica
Authors: Silva Fabiana Laranjeira da , Souza Ana Lívia Siqueira , Leite-Salgueiro Claudia Daniele Barros , Barbosa Luciclaudio Da Silva , Lobato Luzineide , Pereira Juliane Da Silva
Published: August 2018

Este estudo teve como objetivo analisar na literatura, as ações de Assistência e Promoção à Saúde da Mulher praticadas pela enfermagem, com ênfase na fase reprodutiva, nos períodos do pré-natal, do parto e do puerpério, e considerando-se a vivência de abuso e violência obstétrica. Para tanto, fora utilizada a metodologia de revisão integrativa da literatura, tendo sido utilizados para análise e segundo critérios de inclusão, 11 artigos publicados nas bases SciELO, LILACS e MEDLINE, publicados entre os anos de 2008 e 2017. Na análise dos resultados obtidos, os artigos analisados discorrem sobre a Política Nacional de Humanização do Parto e do Nascimento (PNHPN), os direitos da mulher nas fases reprodutivas e vivências considerando a complexidade temática. Conclui-se que a vulnerabilidade biopsicossocial das mulheres é potencializada principalmente nas fases do pré-natal e do parto, maximizando os déficits de ações em saúde, principalmente no tocante à humanização, destacando a atuação do enfermeiro para a garantia dos direitos dessa população específica.
Jordanian Discriminatory Laws Concerning Women. The Dichotomy of Strive for Progression versus Tradition
Authors: Foksa-Biegaj Agata Julia
Published: August 2018

The primary aim of this article is to illustrate the dichotomy of Jordan as a progressive country, perhaps best exemplified through the engagement of the royal family in human rights matters, versus the traditional approach, sanctioning the discriminatory laws concerning women. This paper further attempts to demonstrate that Jordan is balancing between the conservative tribal interests, by pertaining to the Arab and Islamic tradition on the one hand, and the need for democratisation and further human rights development on the other. It is important to note, that discriminatory laws concerning women are not the only examples illustrating this peculiar mechanism, however, they constitute the most vivid one. The author further submits that many authors, as well as international bodies such as CEDAW and the Human Rights Committee, fail to understand the dynamics and complexity of the human rights situation in Jordan. Hence, these authors and authorities’ recommendations are often misguided, as they focus mostly on amending the discriminatory legislation. This article briefly discusses cultural relativism aspects and suggests that actual progress can be achieved by developing a unique language of human rights related to the Arab culture, for instance through the newly established Jordanian Constitutional Court.
Crystal structure of ethyl 2-amino-4-(3,5-difluorophenyl)-7-methyl-5-oxo-4H,5H-pyrano[4,3-b]pyran-3-carboxylate, C18H15F2NO5
Authors: Jia Xingang , Song Jing , Cao Jipeng
Published: August 2018

C18H15F2NO5, monoclinic, C2/c (no. 15), a = 26.896(3) Å, b = 9.005(3) Å, c = 13.737(2) Å, β = 94.971(11)°, V = 3314.6(13) Å3, Z = 8, R
gt(F) = 0.0560, wR
ref(F
2) = 0.1823, T = 293(2) K.
Hydrolyse der insektiziden Phosphorsäureester
Authors: Mühlmann R. , Schrader G.
Published: August 2018

Die praktische Brauchbarkeit eines insektiziden Phosphorsäureesters richtet sich weitgehend nach seiner hydrolytischen Beständigkeit.

Mit Hilfe von 32P-markierten Präparaten werden an 21 Stoffen die Hydrolyse-Konstanten im Temperatur-Bereich von 20-70° und im pll-Bereich von 1 - 9 untersucht.
Apiose als Bestandteil der Zellwand höherer Pflanzen
Authors: Beck Erwin , Kandler Otto
Published: August 2018

Experiments on photosynthesis in 14CO2 with Lemna gibba and Lemna minor showed that apiose occurs only in the fraction insoluble in alcohol and water and may be released by hydrolysis. The portion of radioactivity in apiose increases in the course of photosynthesis to about the same extent as that in xylose. This differs markedly from starch (glucose) in which the portion of radioactivity decreases during photosynthesis.

Darkening, following a longer period of photosynthesis in 14CO2, leads to a change in the ratio apiose-14C/glucose-14C and xylose-14C/glucose-14C, respectively, in favour of apiose and xylose. The same is obtained if labeled glucose is fed for a longer period.

It is concluded that apiose is not part of storage material but like xylose part of a cell wall component.
Aminosäureveränderungen in Rinderinsulin durch UV-Bestrahlung
Authors: Siebert W. , Fiore C. , Dose K.
Published: August 2018

Bei der UV-Bestrahlung (2537 Å) des Zn-Insulins beobachtet man für kleinere Dosen (bis 10 Einstein/Mol) eine direkte Korrelation zwischen der Inaktivierung und der Photoreduktion einer der drei Disulfidbrücken. Mit steigender Dosis wird die Quantenausbeute für die Reduktion der Disulfidbrücken (Bildung von SH-Gruppen) sehr klein, dagegen führen dann andere Prozesse zunehmend zur photochemischen Zerstörung der Disulfidbrücken. Für größere Strahlendosen (über 100 Einstein/Mol) ergibt die Extrapolation, daß für die völlige Inaktivierung des Insulins sämtliche drei Cystinreste zerstört werden müssen. Von den übrigen Aminosäuren wird durch Dosen um 100 Einstein/Mol nur der Tyrosin-Anteil signifikant vermindert. Mit steigender Strahlendosis ändert sich — wahrscheinlich infolge von Konformationsänderungen der Polypeptidketten — die Photosensibilität der Aminosäuren.
Chloramphenicol-Wirkung auf eine durch Licht stimulierte Proteinsynthese in Blättern und in isolierten Chloroplasten
Authors: Parthier B.
Published: August 2018

The antibiotic, chloramphenicol, inhibits the in vivo uptake and incorporation of 35S-methionine into bulk proteins in light and in dark. RNA synthesis is not primarily reduced by inhibitor treatment. There is good evidence that the suppression of substance uptake is due to a previous inhibition of protein synthesis. It has been shown that chloramphenicol blocks the synthesis of chloroplast-protein in light far more strongly than the protein synthesis of other subcellular fractions. There is a slight but constant inhibition of the amino acid incorporation into the proteins of isolated chloroplasts or chloroplast-ribosomes. However, some problems concerning the role of light and the antibiotic interference on the poly-U-stimulated phenylalanine incorporation in these systems remain yet unsolved. Chloramphenicol has no effects on the photosynthetic activities in isolated chloroplasts of mature leaves.
Study of the Dependence of Photosynthetic Yields on the Water and Mineral Supply
Authors: Abdel-Wahab M. F. , Hassan H. M. , Megahid Y. M. , Sobhy C. M.
Published: August 2018

The dependence of photosynthetic yields on both sodium adsorption ratio and osmotic pressure of irrigation water is discussed. As a first example, Zea mays seedlings were exposed to C14O2 in closed photosynthetic chambers for 24 hrs. The chromatographic study of aqueous and alcoholic extracts as well as the hydrolyzed tissue are shown in special tables. Other data concerning respiration rate as well as carbohydrates and mineral metabolism are also studied.

The respiration of two weeks old seedlings of Zea mays is compared with the photosynthetic process.
Anaerobe Vermehrung von Poliomyelitisvirus
Authors: Luthardt Th.
Published: August 2018

The kinetic course of poliomyelitis virus production in monolayer cultures of monkey kidney cells is studied by assaying the cell-associated and free virus as well as by observing the cytopathic changes (CPE).

The virus production in absence of oxygen is decreased to about 1% of that under aerobic conditions. Only a small part of intracellular virus, usually less than 10%, is released from the cells.

The typical cytopathic changes do not occur under anaerobic conditions.

The latent period of virus development is not altered in anaerobically maintained cultures.

If anaerobiosis is interrupted within the first three hours after infection, virus replication and development of CPE occur in the same degree as under uninterrupted aerobic conditions. The reactions sensitive to lack of oxygen take place during the second half of the virus growth cycle (4th to 6th hour). The virus release is not influenced by the presence or absence of oxygen, provided the cells were able to synthetize sufficient amounts of virus under aerobic conditions.

The reduced virus production under anaerobic conditions is not caused by the diminished efficiency of the glycolytic metabolism. The reactions sensitive to lack of oxygen are so far unknown.
Die Stomata als Glieder eines schwingungsfähigen CO2-Regelsystems Experimenteller Nachweis an Zea mays L.
Authors: Raschke Klaus
Published: August 2018

Using recording porometer techniques, evidence was produced for the existence of a regulatory system stabilizing the carbon dioxide concentration within the intercellular spaces of leaves. The guard cells function as effectors, and most probably also as sensors. Measurements by the cells of the carbon dioxide concentration and stomatal movement are two separate processes; the second requires auxiliary energy. The system reacts to disturbances after a time lag. This causes overshoot. Additional strong feedback may lead to stomatal oscillations which sometimes persist, or even increase in amplitude indicating insufficient damping.
Zur Kristallgitterstruktur der sogenannten Prolamellarkörper in Proplastiden etiolierter Bohnen
Authors: Wehrmeyer Werner
Published: August 2018

The spatial arrangement of tubules building up the prolamellar bodies of proplastids in etiolated bean leaves was investigated by electron microscopy. The basic unit of this arrangement is the tetrahedron *, joining to uniplanar five-membered rings with slightly distorted angles and sixmembered strainless rings designated “chair-form” and “boat-form” (following the nomenclature of the two stereoisomeres of cyclohexane in organic chemistry). The center of the concentric prolamellar bodies is held by a pentagonal dodecahedron. This pentagonal dodecahedron and its environment in the direction of the 6 pentagonal axes are built up by five-membered rings combinated with the six-membered boat-form. The chair-form fills up the intermediate spaces and increases in number removing off the center. As the central pentagonal dodecahedron has six fivefold, ten threefold, and fifteen twofold axes, ultrathin sections of the concentric prolamellar bodies show corresponding 532-symmetry provided that the cutting plane meets one of these axes at right angle.
Eine anschauliche Deutung der Mullikenschen „overlap-population“
Authors: Dunken H. , Müller H. , Heegn H.
Published: August 2018

Im Rahmen der Mullikenschen Elektronen-Populations-Analyse 1 wird der Begriff der „Bindungsregion“ erörtert und die Frage nach der Zahl und der räumlichen Verteilung der die Bindung realisierenden Elektronen am Beispiel der gleichkernigen zweiatomigen Moleküle der ersten Achterperiode beantwortet.
Einfluß der thermischen Vorbehandlung auf das Kristallisations-Verhalten des Selens
Authors: Eckart F. , Vogel C. H.
Published: August 2018

Das Kristallisations-Verhalten des glasigen amorphen Selens bei der thermischen Umwandlung der amorphen in die hexagonale bis zum Schmelzpunkt thermodynamisch stabile Phase wird ebenso wie die damit eng verknüpften physikalischen Eigenschaften von den verschiedensten Faktoren, insbesondere vom Reinheitsgrad, von der Dotierung und auch von der thermischen Vorbehandlung beeinflußt.

Da die Umwandlung der amorphen in die hexagonale Modifikation exotherm verläuft, ist es mit Differential-Thermo-Analysen (DTA) möglich, die auftretenden Wärmetönungen zu bestimmen. Bereits früher 1 wurde der Einfluß der Chlordotierung auf das Kristallisations-Verhalten von hochgereinigtem Selen untersucht und gefunden, daß Chlordotierungen den Kristallisations-Verlauf entscheidend beeinflussen 2.

Der Einfluß der thermischen Vorbehandlung auf das Kristallisations-Verhalten von hochgereinigtem Selen wurde im folgenden näher untersucht.
Über die Bildung von Cyanocobalamin aus Aquocobalamin und Cyano-aquo-Corrinoiden
Authors: Friedrich Wilhelm , Bieganowski Rainer
Published: August 2018

Durch Erwärmen von Aquocobalamin mit Cyano-aquo-Corrinoiden (vor allem mit Tetracarbonsäure) in wäßriger Lösung bzw. in 90-proz. Äthanol im Dunkeln wird Cyanocobalamin gebildet. Die Reaktionsgeschwindigkeit hängt sehr stark vom pH und vom Gas ab, das zur Sättigung des Milieus verwendet wurde. Luft und O2 hemmen die Reaktion, vermutlich durch die Bildung eines O2-Adduktes mit (dimerem) Aquocobalamin. CO wirkt stark beschleunigend, vor allem im schwach sauren pH-Bereich. In Gegenwart von N2, H2 und CO2O2 verläuft die CN-Übertragungs-Reaktion bei pH 3 äußerst langsam, bei pH 7 mittelschnell. Die Übertragungsreaktion wird durch Licht nicht beeinflußt.
Strukturen cäsiumhaltiger Fluoride, II1 Die Kristall- und Magnetische Struktur von CsFeF4 / Crystal and Magnetic Structure of CsFeF4
Authors: Babel D. , Wall F. , Heger G.
Published: August 2018

The results of an X-ray structure determination on single crystals of CsFeF4 are reported. The compound crystallizes tetragonally with α = 7.794, c = 6.553 Å, z = 4, in spacegroup P4/nmm-D4h
7 and is a hitherto unknown superstructure variant of the TlAlF4-type. Cesium exhibits 12-coordination (mean value Cs-F = 3.25 Å); the FeF6-octahedra are characteristically shortened normal to the FeF4⁻-layers (Fe-F = 1.962/1.861Å). An improved model is proposed and verified for a related structure of RbFeF4, showing the same features. Neutron diffraction studies on powder samples of CsFeF4 show that both compounds are identical as for their magnetic structures.
Metallkomplexe mit anionischen Liganden von Elementen der 4. Hauptgruppe, VI1.
Authors: Kruck Thomas , Molls Werner
Published: August 2018

Mo(CO)6 reacts with [N(C2H5)4][GeCl3] (1) in refluxing tetrahydrofurane or benzene to form [N(C2H5)4][Mo(CO)5GeCl3] (2). At room temperature the reactions of Ni(CO)4 and 1 form [N(C2H5)4][Ni(CO)3GeCl3] (3) in CH2Cl2 and the disubstituted anion [Ni(CO)2-(GeCl3)2]2- in tetrahydrofurane. The substitution of the aromatic ligand of mesitylene molybdenum tricarbonyl succeeds in boiling CH2Cl2 and yields [N(C2H5)4]3[Mo(CO)3-(GeCl3)3] (4). Even two aromatic rings can be exchanged if dibenzenechromium is refluxed in acetone with 1. The yellow metalate(O) complex [N(C3H5)4]6[Cr(GeCl3)6] (5) is formed with 7% yield only.
Halogenide der Pentafluorphenylthiophosphonic und -thiophosphinsäure / Halides of Pentafluorophenylthiophosphonic and -thiophosphinic acid
Authors: Fild Manfred , Stankiewicz Thomas
Published: August 2018

The thiophosphonic and thiophosphinic halides, C6F5P(S)X2, (C6F5)2P(S)X, and R(C6F5)P(S)X (X = F, Cl, Br, and R = CH3, C2H5, tert-C4H9, C6H5) have been prepared, a) by addition of sulfur to the phosphorus(III) derivatives, b) by the reaction of chlorophosphoranes with H2S, and c) by halogen exchange reaction. The 31P- and 11F NMR data are discussed.
Über Oxocuprate, ΧΧΙII Zur Kenntnis von Ho2Cu2O5 / On Oxocuprates, XXIII About Ho2Cu2O5
Authors: Freund H.-R. , Müller-Buschbaum Hk.
Published: August 2018

Single crystals of the compound Ho2Cu2O5 were obtained by melting the oxide mixture (2 CuO : 1 Ho2O3), using KF as a flux. The crystal structure was investigated by single crystal X-ray data (Space group C2v
9-P 21 nb, lattice constants: a = 1247.8, b = 1081.3, c = 349.5 pm).
2-Vinyl-1.3-dioxolenium- und 4-Methyl-γ-lactonium-Spezies aus Ethylenacetalderivaten via Elektronenstoßionisation / Electron Impact Induced Formation of 2-Vinyl-1,3-dioxolenium- and 4-Methyl-γ-lactonium Species from Ethylenacetal Derivatives
Authors: Bornowski Hans , Feistkorn Volker , Schwarz Helmut , Levsen Karsten , Schmitz Peter
Published: August 2018

The structures as well as the genesis of the C5H7O2
+ ions from some different ethylenacetal derivatives have been established. It is shown that the title ions do not isomerize to a common intermediate or a mixture of equilibrating structures prior to or during collisional activation.
Über die Reaktionen von ein- und zweikernigen, kationischen η5-Cyelopentadienyl-carbonyl-Komplexeii des Eisens, Rutheniums und Osmiums mit flüssigem Ammoniak [1] / On the Reactions of Mono- and Dinuclear, Cationic η5-Cyclopentadienyl Carbonyl Complexes of Iron, Ruthenium and Osmium with Liquid Ammonia [1]
Authors: Behrens Helmut , Jungbauer Anton
Published: August 2018

The covalent carbamoyl compounds η5-C5H5Ru(CO)(L)(CONH2) (L = CO, MeCN, MeNC, PPh3, PEt3) and η5-C5H5Os(CO)2(CONH2) are formed by the reactions of the cationic complexes [η5-C5H5Ru(CO)2(L)]+ (L = CO, MeCN, MeNC, PPh3, PEt3) and [η5-C5H5Os(CO)3]+ with liquid NH3 below 10 °C. In contrast, the reaction of [η5-C5H5Ru(CO)2(η2-C2H4)]PF6 with liquid NH3 yields the quarternary ammonium salt [η5-C5H5Ru(CO)2(CH2CH2
⊕NH3)]PF6. With the cationic complexes {[η5-C5H5M(CO)2]2(P̑P)}++ (M = Fe, Ru; P̑P = Ph2PCH2CH2PPh2) it was possible to prepare the dinuclear P̑P bridged carbamoyl derivatives [η5-C5H5M(CO)(CONH2)]2(P̑P).
Pyrido [2,3-d] thieno [3,2-b] [6H]thiopyran - ein neues heterocyclisches Ringsystem [1] / Pyrido [2,3-d]thieno[3,2-b] [6 H]thiopyran - a New Heterocyclic Ring System [1]
Authors: Beelitz Klaus , Praefcke Klaus , Gronowitz Salo
Published: August 2018

UV irradiation of S-(3′-thienyl)2-chloro-thionicotinate (1) in benzene solution leads via dehydrohalogenation and cy clization in competition to α-cleavage to formation of thio-lactone 2 besides aldehyde 3 and disulphide 4. 2 contains a new heterocyclic ring system which has been confirmed by spectroscopic methods.
N-Chlor-alkanammonium-hexachloroantimonate(V) Spektren und Struktur/ N-Chloro Alkaneammonium Hexachloroantimonates(V) Spectra and Structure
Authors: Thiel Norbert , Schwarz W. , Schmidt A.
Published: August 2018

N-Alkyl-N-chloro and N-chloro alkaneammonium hexachloroantimonates(V) are prepared by reaction of N-alkyl-N-chloro and N,N-dichloroalkaneamines, resp., with hydrogenchloride/antimony(V) chloride (R = Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, t-Bu). 1H n.m.r. and the vibrational spectra are measured and NCI vibrations of the chloro alkaneamines, which exist in different rotational isomers, are reported. The crystal and molecular structure of the N-ethyl-N-chloro ethylammonium hexachloroantimonate(V) (2) is determined by X-ray analysis.
Darstellung und Aufbau von HfP2S6 / Preparation of HfP2 S6
Authors: Simon A. , Hahn H. , Peters K.
Published: August 2018

Hafnium Hexathiohypodiphosphate, Crystal Structure HfP 2 S 6 is prepared from the elements at temperatures between 500 and 900 °C. The single crystal X-ray analysis reveals isotypism (Fdd2, a = 1100.7(3), b = 747.6(2), c = 2200.8(4) pm) with TiP 2 S 6 .
NMR-spektroskopische Untersuchungen an Chalkogenverbindungen, VI [1]. 34S-Isotopeneffekte auf 19F-NMR-Frequenzen und ihre Abhängigkeit von Bindungslängen / NMR Spectroscopic Studies on Chalcogen Compounds, VI [1] l4.34S Isotope Effects on 19F-NMR Frequencies and their Dependence on Bond Lengths
Authors: Gombler Willy
Published: August 2018

Nineteen values for 34S-induced isotope shifts on the NMR frequency of directly bonded fluorine of fourteen S(II), S(IV), and S(VI) compounds are reported. The dependence of these 1Δ19F(34/32S) values on the S-F bond length is demonstrated. Three reasons for this correlation are discussed. (1) A nonlinear dependence of nuclear shielding on bond distance. (2) Decreasing energy difference of two isotopomers with increasing bond distance. (3) Decreasing anharmonicity of the potential curve with increasing bond length. Some previously unknown S-F bond distances have been estimated by this correlation. The isotope shifts decrease with increasing temperature. This is attributed to vibrationally excited states in conjunction with a nonlinear dependence of nuclear shielding on bond distance. Furthermore, 34S-induced isotope shifts on fluorine-19 over two bonds, 2Δ19F(34/32S), have been observed for the first time, and the 33S-induced isotope effect in SF6 has been measured.
Thioharnstoff-Derivate als Liganden in Eisen-Komplexen: Synthese und Kristallstrukturen von [FeI2L2], [Fe2I4L3], (L -L)2+[FeI4
-]2 (L = (Me2N )2CS) und [Fe2I4(C6H10(NH-CS -NHMe)2)2] mit einer Notiz zu [FeIL3]+[Fe4S4I3L]-/Thiourea Derivatives as Ligands in Iron Complexes: Syntheses and Crystal Structures of [FeI2L2], [Fe2I4L3], (L -L)2+[FeI4
-]2 (L = (Me2N )2CS) and [Fe2I4(C6H10(NH-CS -NHMe)2)2] and a Note on[FeIL3]+[Fe4S4I3L]-
Authors: Bierbach Ulrich , Saak Wolfgang , Haase Detlev , Pohl Siegfried
Published: August 2018

[FeI2L2] (1) and [Fe2I4L3] (2) are obtained from the reaction o f FeI2 and 1,1,3,3-tetramethylthiourea

(L) in tetrahydrofuran solution. The Fe(III) complex [FeI3L] (3) and iodine react in dichloromethane to give (L-L )2+[FeI4-]2 (4). The bidentate thiourea derivative C6H10(NH - CS -NHMe)2 (5) reacts in acetonitrile solution with Fel2 producing the dinuclear

complex [Fe2I4(C6H10(NH - CS -NHMe)2)2] (6).

1 and 2 were obtained in nearly quantitative, 4 and 6 in good (ca. 87%) yield.

The structures of 1, 2 ,4 and 6 were determined from single crystal X-ray diffraction data.

1 crystallizes in the monoclinic space group C 2/c with a = 1862.5(1), b = 1084.0(1), c = 1433.4(1) pm, β = 134.01(1)°. V = 1994.69 x 106 pm3, Z = 4, conventional R 0.055. The complex exhibits a two-fold symmetry and a distorted tetrahedral coordination of Fe(II).

2: monoclinic, C 2/c, a = 1968.9(2), b = 902.8(1), c = 2222.4(2) pm, β = 123.35(1)°, V = 3299.91 x 106 pm3, Z = 4, conventional R 0.036. The metals of the dinuclear complex of 2 are sulfur-bridged with distorted tetrahedral coordination of Fe(II). The bridging sulfur lies on a two-fold axis.

4: monoclinic, P21/c, a = 1135.3(2), b = 1791.9(5), c = 1642.1(4) pm, β = 93.53°, V = 3334.00 x 106 pm3, Z = 4, conventional R 0.044. The mean Fe -I bond length within the tetrahedral Fel4
- anions is 254.1 pm. The (Me2N)2CS - S(NMe2)2
2+ cation exhibits a CS - SC dihedral angle of 75.9° and an S - S bond length o f 205.2(4) pm.

In the dinuclear complex of 6 two bidentate ligands coordinate two FeI2 units in such a way

that a central eighteen-membered ring is formed. The complex shows a two-fold symmetry.

Angles at the (pseudotetrahedral) metal range from 102.1(1) to 118.2(1)°.

The reported synthetic and structural studies and the isolation of [FeIL3]+[Fe4S4I3L]- (7) indicate

that thiourea derivatives seem to be useful ligands for the stabilization o f neutral Fe -S clusters.
Mannich Reaction with 1 ,3 - Indandione Phenylhydrazones
Authors: Afsah E. M. , Hammouda M. , Zoorob H. , Khalifa M. M. , Zimaity M. T.
Published: August 2018

Mannich reaction of 1,3-indandione-1-phenylhydrazone (1) or 1,3-diphenylhydrazone (5) with

morpholine or piperazine gave the Mannich base-phenylhydrazone 2 and 3 or the diphenylhydrazone

6 and 7, respectively. Whereas, such reaction with 1 or 5 using primary amines afforded

the indeno[2,1-ƒ]-1,2,4-triazepin-6(2H)-one (4) or its 6-phenylhydrazone (8), respectively.

Treatment of 5 with ammonium acetate and formalin afforded 9. The indeno[1,2-ƒ]-1,2,4,5-

tetrazepin-10(2H)-one (11) was obtained from the 1,2-diphenylhydrazone 10 and formaldehyde.
Ca4Ni3C5, a Carbide with an One-Dimensionally Infinite Nickel-Carbon Polyanion, and CaPd3C, a Perovskite Carbide
Authors: Musanke Uwe E. , Jeitschko Wolfgang
Published: August 2018

The new carbides Ca4Ni3C5 and CaPd3C were prepared from the elemental components by arc melting and subsequent annealing at 700 °C. The structure of Ca4Ni3C5 was determined from single-crystal X-ray data. It crystallizes in the monoclinic space group C2/m, a = 1108.7(3) pm, b = 377.1(1) pm, c = 983.9(2) pm, β = 112.58(2)°, Z = 2. Powder data show CaPd3C to have the cubic perovskite structure with a = 414.1(2) pm. While the carbon atoms in CaPd3C are isolated from each other, they form C2 pairs in Ca4Ni3C5 with the typical triple bond C-C distance of 120(2) pm. In addition to the C2 pairs there are isolated carbon atoms in distorted octahedral coordination of four Ni atoms forming a square, which is augmented by two Ca atoms. In the one-dimensionally infinite polyanion [Ni3C5]n
8n- these CNi4 squares are condensed by sharing two Ni atoms at opposite corners of the squares. A C2 pair is attached to each of the other Ni atoms in an end-on configuration. Chemical bonding within this polyanion is briefly discussed on the basis of the 18- and 8-electron rules for the Ni and C atoms, respectively. Ca4Ni3C5 is diamagnetic with a susceptibility of χ = – 12(± 5) × 10-9 m3/mol.
Von organometallisch substituierten Alkenylboranen zu Alienen und 3-Borolenen / From Alkenylboranes Bearing Organometallic Substituents to Alienes and 4-Borolenes
Authors: Wrackmeyer Bernd , Locquenghien Klaus Horchler von
Published: August 2018

Alkenylboranes bearing organometallic substituents (E)—Me3M(R1)C=C(Et)BEt2 [M = Sn, R1 = H (la), Me (lb); M = Pb, R1 = Me (2a), PbMe3 (2b)] react with alkynyllead compounds Me3Pb—C=C—R2 [R2 = Me (3a), 'Bu (3b), PbMe3 (3c)] to give either alienes (5) or 3-borolenes (7), depending on the nature of R2. 3-Borolenes are observed for R2 = Me and diene derivatives were identified in the reaction mixtures as intermediates, consistent with mechanistic suggestions. Only one of the two possible diastereomers of the allene 5b (from la and 3b) is formed. The products have been characterized by multinuclear NMR spectroscopy (1H,11 B,13C, 119Sn and 207Pb NMR). In the case of 5c (from 2b and 3c), a homonuclear two-dimensional 207Pb COSY NMR spectrum serves for the assignment of the 207Pb resonances of diastereomers.
Oxidations of Alkylbenzenes with Dimethyldioxirane
Authors: Kuck Dietmar , Schuster Andreas
Published: August 2018

The oxidation of various alkylbenzenes (1-17) with excess dimethyldioxirane (DMDO) in homogeneous acetone solutions has been studied. In general, the benzylic methylene and methine C–H bonds were oxidized to give the corresponding phenones and tertiary benzylic alcohols, respectively, in relatively low yields. Whereas a tert-butyl substituent at the reaction centre leads to very low conversion due to steric hindrance, the presence of additional phenyl groups appears to favour the oxidation in most, but not all cases. Di- and triphenylmethane (4 and 14) were found to be considerably less reactive than cis-decalin. By contrast, the intramolecular competetive oxidation of isobutylbenzene (19) and 1-methyl-4-phenylcyclohexanes (20) reveals that the benzylic C–H bonds are slightly more reactive than the tertiary ones at remote positions.
Synthese von Cyclopropanphosphonatpyranosiden / Synthesis of Cyclopropylphosphonate Pyranosides
Authors: Fatima Ayjaz , Zaman Fakhar , Voelter Wolfgang
Published: August 2018

Reacting benzyl 2,3-anhydro-4-O-trifluoromethylsulfonyl-α-D-ribopyranoside (1) and benzyl 2,3-anhydro-4-O-trifluoromethylsulfonyl-β-L-ribopyranoside (2) with diethyl cyanomethylphosphonate the 3,4-cyclopropanated monosaccharide derivatives benzyl 3,4-(diethyl cyanomethylenephosphonate)-3,4-dideoxy-β-L-arabinopyranoside (5) and benzyl 3,4-(diethyl cyanomethylenephosphonate)-3,4-dideoxy-β-L-arabinopyranoside (6) are obtained. The 1H, 13C NMR and FD-MS data fully confirm the suggested structures. The cyclopropanated sugar derivatives are of interest because of their structural relation to the antibiotic phosphonomycin.
Komplexbildung und Metallextraktion mit heterocyclischen β-Dicarbonylverbindungen im Vergleich. Struktur von 3-Phenyl-4-benzoyl-isoxazol-5-on / Complex Formation and Metal Extraction with Heterocyclic β-Dicarbonyl Compounds as Comparison. Structure of 3-Phenyl-4-benzoyl-5-isoxazolone
Authors: Uhlemann Erhard , Friedrich Alwin , Hinsche Gerald , Mickler Wulfhard , Schilde Uwe
Published: August 2018

Acid constants and stability constants of nickel and zinc chelates with 2-thenoyltrifluoroacetone, dibenzoylmethane, 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone and 3-phenyl-4-benzoyl-5-isoxazolone were compared. The extraction of copper was studied. Thermoanalytic measurements were made using the ligands and their copper compounds in the solid state. The molecular structure of 3-phenyl-4-benzoyl-5-isoxazolone was determined by X-ray analysis. Crystal data: a = 874,7(2), b = 1959,2(7), c = 897,38(7) pm; β = 101,030(7)°; space group P 121/c 1; Z = 4; R = 0,043; 1920 observed, unique reflexions.
Einkristallröntgenstrukturanalyse an Quecksilberchromat(VI): Hg3O2CrO4 / Single Crystal X-Ray Structure Determination of a Mercury Chromate(VI): Hg3O2CrO4
Authors: Hansen Th. , Müller-Buschbaum Hk. , Walz L.
Published: August 2018

Single crystals of Hg3CrO6 have been prepared by high pressure techniques (3600 bar oxygen, 600 °C). Hg3CrO6 crystallizes with trigonal symmetry, space group D6
3—P3212, a = 7.137(1), c = 10.017(2) Å, Z = 3. Nearly linear O—Hg—O dumb-bells are connected in planes, forming strongly puckered nets of six-membered rings. Each Hg6O6 ring is centered by a CrO4 tetrahedron; the CrO4 tetrahedra are arranged in two equally occupied split positions.
Synthese und Kristallstrukturen von Diazadien-Komplexen der Erdalkalimetalle / Syntheses and Crystal Structures of Diazadiene Complexes of the Alkaline Earth Metals
Authors: Lorenz Volker , Neumüller Bernhard , Thiele Karl-Heinz
Published: August 2018

(DME)2] 1 (R = C6H4-4-CH3; DME = dimethoxyethane) was prepared by reaction of calcium with NR=CPh-CPh=NR in DME solution. The compound forms orange, moisture sensitive crystals, which were characterized by an X-ray structure determination [space group orthorhombic, P212121, Z = 4, 4634 observed unique reflections, R = 0.046; lattice dimensions at –70 °C: a = 1340.2(3), b = 1528.1(3), c = 1609.1(3) pm]. The calcium atom is coordinated by the four oxygen atoms of two chelating DME molecules and two nitrogen atoms of the diazadiene ligand, bonded in its enediamide form.

[Ba2(DME)3(NPh–CPh=CPh–NPh)2 · DME] 3 was obtained from barium metal and NPh=CPh-CPh=NPh in DME solution as red crystals [space group monoclinic, P2l/c, Z = 4, 4000 observed unique reflections, R = 0.166; lattice dimensions at -70 °C: a = 1704.5(3), b = 1786.1(4), c = 2177.4(4) pm, β = 105.98(3)°]. The two barium atoms are bridged by two differently bonded diazadiene ligands (μ2-Ν,Ν′;μ-Ν, σ-Ν′). Additionally, one of the barium atoms is coordinated to two DME molecules and the other one to only one of the ether molecules. A further DME molecule is a constituent of the crystal lattice.
Lithium- [N-di-tert-butylfluorsilyl-N′,Ν′-dimethyl-hydrazid] -Synthese, Kristallstruktur und Reaktivität / Lithium (N-di-tert-butylfluorosilyl-N′,N′-dimethyl)hydrazide -Synthesis, Crystal Structure and Reactivity
Authors: Drost Christian , Jäger Carsten , Klingebiel Uwe , Freire-Erdbrügger Christina , Herbst-Irmer Regine , Schäfer Martina
Published: August 2018

Di-tert-butyldifluorosilane reacts with N-lithium-N′,N′-dimethylhydrazine in a molar ratio 1:1 to yield the N-di-tert-butylfluorosilyl-N′,N′-dimethylhydrazine 1. The lithium derivative of 1 (2) forms a dimer with the nitrogen atoms coordinated “side-on” to the lithium atoms. The silylation with Me3SiCl gives product 3. Heating 2 in a vacuum leads to the cyclodisilazane derivative 4. A bis(hydrazino)fluoroborane (5) is obtained in the reaction of 2 with trifluoroborane-etherate.
Polysulfonylamine, LXIII [1] / Polysulfonylamines, LXIII [1]
Authors: Henschel Dagmar , Blaschette Armand , Jones Peter G.
Published: August 2018

Complexes of Uncharged Molecules, Crystal Structure

The thermally labile ternary complexes 18C6 · 2MeOH · 2 HN(SO2Ph)2 (2a), 18C6 · 2MeOH · 2HN(SO2–C6H4-4-Cl)2 (2b) and 18C6 · 3 MeOH · HN(SO2Me)(SO2Ph) (3) were obtained by co-crystallization of 18-crown-6 (18C6) and the appropriate di(organosulfonyl)amine from methanolic solutions and characterized by low-temperature X-ray diffraction. The crystal structures of 2a (monoclinic, space group P21/n) and 2b (triclinic, space group P1̄) consist of monomeric, centrosymmetric formula units. Each di(arenesulfonyl)-amine molecule is connected to a methanol molecule by an N-Η ··· O hydrogen bond (H ··· O 203 pm in 2a, 190 pm in 2b). The methanol molecules are linked to three alternate crown oxygen atoms via one O-Η ··· O(crown) hydrogen-bond and two weaker C-Η ··· O(crown) interactions (OH ··· O 201 pm in 2a, 186 pm in 2b; CH ··· O 236 and 247 pm in 2a, 240 and 254 pm in 2b); two symmetry-related oxygen atoms of the crown are involved in O-Η ··· O and the other four in C-Η ··· O interactions. The structure of complex 3 (monoclinic, space group P21) is built of infinite chains parallel to [101]. The methyl group of the di(organosulfonyl)amine is bonded by C-Η ··· O(crown) interactions to a set of three alternate oxygen atoms of the cyclic polyether (H ··· O 228, 245 and 247 pm). Starting from the acidic NH function, a sequence of three methanol molecules catenated by hydrogen bonds curves around the bulky phenyl group and links with its terminal MeOH through one O-H ··· O(crown) and two C-Η ··· O(crown) bonds to the second set of alternate oxygen atoms in the adjacent symmetry-equivalent crown (OH ··· O 193 pm, CH ··· O 248 and 250 pm). Within the chain sequence N-H ··· O′(Me)H′ ··· O″(Me)H″ ··· O‴(Me)H, the H ··· O distances are H ··· O′ 184, H′ ··· O″ 189 and H″··· O‴ 183 pm. In the structures of 2a, 2b and 3, the crown rings adopt the frequently observed D3d pseudosymmetry.
Structure and Conformation of Photosynthetic Pigments and Related Compounds, 8 [1]
Molecular Structure of an Iron(III) Chlorophyll Derivative-Chloro(phytochlorinato methyl ester)iron(III)
Authors: Senge Mathias O. , Ruhlandt-Senge Karin , Smith Kevin M.
Published: August 2018

The crystal and molecular structure of chloro(methyl phytochlorinato)iron(III), 4, have been determined by single crystal X-ray crystallography to obtain further information on the conformation of metallochlorins related to chlorophyll. The compound crystallized with two independent molecules mainly distinguished by the orientation of the axial ligand. The macrocycles show significant deviations from planarity larger than those observed in corresponding magnesium(II) complexes. The overall type of distortion is similar to those found in chlorophyllides. Compound 4 crystallized in the monoclinic space group P21 (MoKa,λ = 0.71063 A) with unit cell dimensions a = 12.035(6) Å, b = 13.396(8) Å, c = 19.04(2), b = 97.51(2) Å, Z = 4, V = 3043(4) Å3. The structure was refined to an R-value of 0.075 on the basis of 3974 reflections with I > 3.0σ(Ι) (130 Κ).
Berechnung der 19F- und 195 Pt-NMR-Verschiebungen von FIuoro-Chloro-Bromo-Platinaten(IV) / Calculation of 19F and 195Pt NMR Shifts of Fluoro-Chloro-Brom o-Platinates(IV )
Authors: Drews H.-H. , Preetz W.
Published: August 2018

By reaction of [PtBr4]2- with XeF2 in dichloromethane product mixtures containing nine fluoro-chloro-, four fluoro-bromo- and 15 fluoro-chloro-bromo-platinates(IV) are formed. All complexes are detectable by in situ l9F NMR measurements. Due to the increasing trans influence F < Cl < Br, the signals <5(19F) of symmetric F-Pt-F axes observed at highest field are shifted downfield on the average by 93 ppm as compared with δ(19F•) of F••Pt-Cl′ axes, and further to lower field by 40 ppm for <5(F••) of F••-Pt-Br″ axes. For the same reason the coupling constant 1J(F••Pt) ≈ 1099 Hz is by 13.3 % smaller than 1J(F•Pt) ≈ 1268 Hz, which is by 32.3 % smaller than δ(FPt) ≈ 1873 Hz. Based on the axis method, and taking into account characteristic increments of chemical shifts depending on cis influences, the calculation of the 195Pt NMR signals of 27 observed species of the system [PtFnCl6-n-mBrm]2- n, m = 0 - 6, has been successful. The 195Pt NMR shifts of further 29 so far not detected complexes are predicted. Using parameters depending on the geometry of the complex, the 19F NMR shifts of 28 F-containing platinates(IV) have been calculated in good agreement with the experimental data. 19F resonances are predicted for 19 so far missing complexes.
ab-initio-Rechnungen, Schwingungsspektren und Normalkoordinatenanalyse von closo-[B6H5F]2– / ab initio Calculations, Vibrational Spectra, and Normal Coordinate Analysis of closo-[B6H5F]2–
Authors: Steuer B. , Thomsen H. , Preetz W.
Published: August 2018

The structural parameters of closo-[B6H5F]2- with C4v symmetry have been determined by MP2/6-31G* optimization. They reveal typical B-F and B-B bond lenghts of 143.4 and 172.5 -173.9 pm, respectively. A frequency analysis at the same theoretical level has been performed. The vibrational spectra of [B6H5F]2- labelled with 10B, 11B and D have been additionally assigned by normal coordinate analysis based on a modified valence force field using the ab initio structure parameters. With a set of 10 force constants (e.g. fd(BB)=1.92, fd(BF)=5.25 mdyn/Å) a good agreement between observed and calculated frequencies can be achieved. The results correspond with the scaled (Fscale=0.97) ab initio frequencies and assignments.
Isolierte MnCl6-Oktaeder im Oxohalogeno-Vanadat Ba5(Mg0,4Mn0,6)(V2O7)2MnCl6 / Isolated MnCl6 Octahedra in the Oxohalogeno Vanadate Ba5(Mg0,4Mn0,6)(V2O7)2MnCl6
Authors: Rettich R. , Müller-Buschbaum Hk.
Published: August 2018

Single crystals of Ba5(Mg0,4Mn0,6)(V207)2MnCl6 have been prepared by solid state reactions of MgCO3, Mn2O3, V2O5 and BaCl2·2H2O below the melting point of BaCl2. The new vanadium oxide chloride crystallizeswith monoclinic symmetry, space group C4
2h-P2/c, a = 13.345(4), b = 5.711(2), c = 15.859(4) Å, β = 113.69(2)°, Z = 2. Special features of the crystal structure are isolated MnCl6 octahedra and layers created by divanadat groups and (Mg,Mn)O6 octahedra. The 2
∞ [(Mg,Mn)V2O7] nets of Ba3(Mg0,4Mn0,6)(V2O7)2MnCl6 are discussed with respect to other oxohalogeno vanadates Containing divanadate groups.
Silaheterocyclen, XXXIII [1, 2]: Cycloadditions-Reaktionen des 1.1-Dichlor-2-neopentyIsilaethens mit Pentafulvenen / Silaheterocycles, XXXIII [1, 2]: C y clo ad d itio n Reactions of 1.1-Dichloro-2 -neopentylsilene with Pentafulvenes
Authors: Auner Norbert , Heikenwälder Claus-Rüdiger
Published: August 2018

The reaction between in situ formed 1.1-dichloro-2-neopentyl-1-silene, Cl2Si=CHCH2tBu (2), and 1,1-dimethylpentafulvene (5) leads to the formation of exo/endo-isomeric [4+2] cycloadducts 9 and [2+2] stereoisomers 10 in good yields. NMR spectroscopic investigations of the product mixture prove the different modes of the silene cycloaddition reactions ([4+2] vs [2+2] addition).

Treatment of 9 and 10 with LiAlH4 and LiMe yield the stereo- and regioisomeric derivatives (LiAlH4: 16, 17: MeLi: 18. 19). whereas PhMgBr reacts with 10 to give only the mono substitution, the [4+2] compound 20. and the diphenylated silacyclobutane 21. The reactions of silene 2 with pentafulvenes 6-8 lead to similar results.
Kantenverknüpfte VO6-0ktaeder und PO4-Tetraeder in BaCa(VO)(PO4)2 / Edge-Connected VO6 Octahedra and PO4 Tetrahedra in BaCa(VO)(PO4)2
Authors: Meyer S. , Müller-Buschbaum Hk.
Published: August 2018

Abstract Single crystals of the new compound BaCa(VO)(PO4)2 have been prepared by solid state reactions below the melting point of the reactants in evacuated quartz tubes. X-ray investigations led to monoclinic symmetry, space group C2h
5 - P21/c, a = 7.300(1), b = 7.053(1), c = 14.460(1) Å, β = 101,43(1)°, Z = 4. The crystal structure is characterized by layers of corner-and edge-connected PO4 tetrahedra and VO1+5 octahedra. There is an unusually short O(1)-O(4) distance in a VO6 octahedron of 2.44 Å associated with the sharing of edges with PO4 tetrahedra. The short V-O distance of 1.61 Å indicates a vanadyl group.
Zur Reaktion von Derivaten des 1,3-Dimethyl-2-iminoimidazolins mit CS2 [1] / On the Reaction of 1,3-Dimethyl-2-iminoimidazoline Derivatives with CS2 [1]
Authors: Kuhn Norbert , Fawzi Riad , Steimann Manfred , Wiethoff Jörg
Published: August 2018

1,3-Dimethyl-2-iminoimidazoline (4, ImNH) reacts with CS2 to give the imidazolium salt [ImNH2][(ImNCS2)2H] (7) in which two dithioformimide fragments are linked by a hydrogen bridge. From the trimethylsilyl derivative ImNSiMe3 (11) and CS2 the adduct ImNSiMe3 • CS2 (12) is obtained which reacts with oxygen to give the disulfide (ImNCS2) (14). The X-ray structures of 7 and 14 were determined.
Chemical Basis for High Activity in Oxygenation of Cyclohexane Catalyzed by Dinuclear Iron(III) Complexes with Ethereal Oxygen Containing Ligand and Hydrogen Peroxide System
Authors: Ito Sayo , Okuno Takashi , Itoh Hiroki , Ohba Shigeru , Matsushima Hideaki , Tokii Tadashi , Nishida Yuzo
Published: August 2018

The crystal structures of two binuclear iron(III) complexes with linear μ-oxo bridge, Fe2OCl2 (tfpy)2 (ClO4)2 ·2CH3CN and Fe2OCl2(epy)2(ClO4)2 were determined, where (tfpy) and (epy) represent N,N-bis(2-pyridylmethyl)-tetrahydrofurfurylamine and N,N-bis(2-pyridylmethyl)-2-ethoxyethylamine, respectively. Their structural features are essentially the same as that of the corresponding linear binuclear complex with (tpa)-complex, Fe2OCl2(tpa)2(ClO4)2, where (tpa) is tris(2-pyridylmethyl)amine; the ligands (tfpy) and (epy) act as a tetradentate tripod-like ligand, and Fe-O (ethereal oxygen atom; these are located at the trans-position of bridging oxo-oxygen atom) distances are 2.209(4) and 2.264(2) Å for (tfpy) and (epy) compounds, respectively. These two (tfpy) and (epy) complexes exhibited much higher activity for the oxygenation of cyclohexane in the presence of hydrogen peroxide than that of the (tpa) complex. In contrast to this, the former two complexes exhibit negligible activity for the decomposition of hydrogen peroxide, whereas the catalase-like function of the (tpa) compound is remarkable. These are indicating that an active species for oxygenation of cyclohexane, which is assumed to be an iron(III)-hydroperoxide adduct with η1-coordina­tion mode, should be different from that is operating for decomposition of hydrogen perox­ide; for the latter case formation of a (μ-η1:η1-peroxo)diiron(III) species being stressed. The EHMO calculation showed that electronic interaction between the monodentate hydroperox­ide adduct of the binuclear iron(IIl)-(tfpy) compound and the tetrahydrofuran ring of the ligand system may lead to facile peroxide-tetrahydrofuran linkage formation, and the interac­tion described above should promote the O-O cleavage of the peroxide ion heterolytically. Based on these discussions, it was concluded that heterolytic O-O bond cleavage of the iron(III)-hydroperoxide adduct caused by electronic interaction with organic moiety contain­ing an ethereal-oxygen and by approach of the substrate which donates electron to the perox­ide adduct should play an important role in producing a high-valent iron-oxo species in these systems. In the case of (tpa) complex, formation of a hydroperoxide adduct linking with the ligand system seems to be unfavorable because of both the steric and electronic reasons.
Novel Electrochemically Derived Dimers of Methylated Uracils
Authors: Bojarska Elżbieta , Kamiński Jarosław , Stolarski Ryszard , Kazimierczuk Zygmunt
Published: August 2018

Electrolysis of acetic acid/sodium acetate solutions of N-methylated uracils results in the formation of 5-substituted methyl and acethoxy derivatives. Electrolysis of trifluoroacetic acid/potassium trifluoroacetate solutions of N-1-and N-3-methylated uracils provided, be­ sides 5-trifluoromethyl derivatives, novel N-C uracil dimers. In the case of 1,3-dimethyluracil in trifluoroacetic acid. N-l demethylathion was also observed.
Notizen: [{Cp*(CI)Re}2(μ-CO)2](Re ≡ Re), ein zweikerniger Rhenium(II)-Komplex mit cis-konfigurierten, terminalen Cl-Atomen/[{Cp*(Cl)Re}2(μ-CO)2](Re ≡ Re), a Dinuclear Rhenium(II) Complex with cis Configuration of the Terminal Cl Atoms
Authors: Scherer Otto J. , Ehses Markus , Wolmershäuser Gotthelf
Published: August 2018

The reaction of [{Cp*(OC)2Re}2](Re = Re) (1), Cp* = C5Me5, with CH2Cl2 yields the dinuclear rhenium complexes [{Cp*(Cl)Re}2(μ-CO)2](Re ≡ Re) (2) with cis orientation of the Cl atoms, [{Cp*(OC)2Re}2(μ-CH2)](Re-Re) (3), a complex with a bridging CH2-carbene ligand, and [{Cp*(OC)2Re}2(μ-C=CH2)]( Re-Re) (4), a μ-vinylidene( alkenylidene) compound. The structure of 2 has been confirmed by a single crystal X-ray structure determination. Starting with [Cp*Re- (CO)2(thf)] (6) instead of 1 the reaction with CH2Cl2 affords cis-[Cp*Re(CO)2(Cl)(CH2Cl)] (7) by oxidative addition of dichloromethane.
Synthese von 2,2-DiphenylethyI-substituierten Silanen -Molekülstruktur von Trichlor-2,2-diphenylethylsilan /Syntheses of 2,2-Diphenylethyl-Substituted Silanes -Molecular Structure of Trichloro-2,2-diphenylethylsilane
Authors: Dautel J. , Abele S. , Schwarz W.
Published: August 2018

Hydrosilylation of 1,1-diphenylethylene with trichlorosilane leads in high yields to trichloro-2.2-diphenylethylsilane (1), which was investigated spectroscopically as well as by X-ray structure determination. The compound crystallizes monoclinically in the acentric space group Cc {a = 1002.4, b = 1573.8, c = 979.7 pm, β = 106.27°, Z = 4}; the bonding parameters show no special features. By fluorination with zinc(II) fluoride in diethylether and by reduction with “Red-Al” in toluene, the corresponding SiF3 (2) and SiH3 derivatives (3) are received, respectively.
Synthese und Kristallstruktur von Perhydro-1,4-benzoxazino[2,3-n]phenoxazin/Synthesis and Crystal Structure of Perhydro-1,4-benzoxazino[2,3-n]phenoxazine
Authors: Kläui Wolfgang , Schoger Susanne , Nieger Martin
Published: August 2018

The oxidation of trans-2-aminocyclohexanol with nitrobenzene in the presence of catalytic amounts of iron inter alia yields perhydro-1,4-benzoxazino[2,3-n]phenoxazine (1). This compound has been characterized analytically, spectroscopically and by X-ray diffraction. It is postulated that the oxidation of the 2-aminoalcohol leads to the intermediate formation of a 1,2-dione. The direct synthesis of 1 from trans-2-aminocyclohexanol and 1,2-cyclohexandione supports this hypothesis.
Enantioselektive Katalyse, 109 Neue erweiterte chirale Bipyridine/Enantioselective Catalysis, 109 New Expanded Chiral Bipyridines
Authors: Brunner Henri , Poleschak Ingo
Published: August 2018

Optically active two and three layer nitrogen ligands were synthesized by reacting the N-BOC-protected aminoalcohols (1S,2S)-2-amino-1 -phenyl-1,3-propanediol and (S)-2-amino-1,4-butanediol with chloromethyl-benzoic acid chlorides. Expansion was carried out at the chlo-romethyl substituents via nucleophilic substitution with N-methylated (R)-1-phenylethylamine. The deprotected substances were N-benzylated and reacted with 6,6′-bis(bromomethyl)-2,2′-bipyridine to give the new optically active expanded bipyridine ligands.