| 141 | Author
| H.-J Kraus, H. Werner, C. Krüger | Requires cookie* | | Title
| Synthese und Struktur von C5Me5Pd(PR3)X: Palladiumkomplexe mit einem unsymmetrisch gebundenen Pentamethylcyclopentadienylring [ 1 ] Synthesis and Structure of CsMe5Pd(PR3)X: Palladium Complexes with an Unsymmetrically Bonded Pentamethylcyclopentadienyl Ring [1]  | | | Abstract
| The complexes C5Me5Pd(PR3)X (1-4) are prepared from [Cl(PR3)Pd]2(iM-OCOCH3)2 and TICsMes. Attempts to replace the halide ligand by a second CsMes or a C5H5 unit remained unsuccessful. The X-ray structure analysis of C5MesPd[P(i-Pr)3]Cl (3) indicates that the five-membered ring shows a tendency of »^-bonding towards the metal. Das Interesse an Pentamethylcyclopentadienyl-metall-Verbindungen ist in den letzten Jahren stän-dig gestiegen, nachdem an zahlreichen Beispielen gezeigt werden konnte, daß die Einführung des CsMes-an Stelle des CsHs-Liganden eine Zunahme der Stabilität der Ring-Metall-Bindung bewirkt [2], In der Reihe der Platinmetalle sind Komplexe mit CsMes vor allem von Rhodium und Iridium darge-stellt und auch strukturell charakterisiert worden; die Arbeiten von P. M. Maitlis und seiner Gruppe haben hier bahnbrechend gewirkt [3]. Im Vergleich dazu ist nur relativ wenig über Pentamethylcyclopentadienylpalladium-Verbindun-gen bekannt. Wir hatten kürzlich gefunden [4], daß bei der Umsetzung der Acetat-verbrückten Zwei-kernkomplexe [Cl(PR3)Pd]2(//-OCOCH3)2 mitTICsHö die Verbindungen (^ 5 -C5H5)Pd(?? 1 -C5H5)PR3 entste-hen, die in Lösung ein fluktuierendes Verhalten zei-gen. Aufgrund von !H-und 13 C-NMR-spektrosko-pischen Messungen sind zwei dynamische Prozesse nachweisbar, wobei der Prozeß mit der größeren Aktivierungsenergie ein nja-(bzw. rf/r] 1 -)-Aus-tausch der beiden unterschiedlich gebundenen Cy-clopentadienylliganden und derjenige mit der kleine-ren Altivierungsenergie eine metallotrope Umlage-rung ist. Die Koaleszenztemperatur für den | | |
Reference
| Z. Naturforsch. 38b, 733—737 (1983); eingegangen am 1. März 1983 | | |
Published
| 1983 | | |
Keywords
| Pentamethylcyclopentadienylpalladium Complexes, Synthesis, Crystal Structure, Bonding Mode | | |
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| default:Reihe_B/38/ZNB-1983-38b-0733.pdf | | | Identifier
| ZNB-1983-38b-0733 | | | Volume
| 38 | |
142 | Author
| Reinhold Tacke, Hartwig Lange, WilliamS. Sheldrick, Günter Lambrecht, Ulrich Moser, Ernst Mutschier | Requires cookie* | | Title
| Sila-Pharmaka, 31. Mitt. [1] Synthese, Struktur und pharmakologische Eigenschaften von Diphenyl(2-piperidinoethoxymethyl)silanol und seinem Kohlenstoff-Analogon Sila-Pharmaca, 31 th Communication [1J Synthesis, Structure, and Pharmacological Properties of Diphenyl(2-piperidinoethoxymethyl)silanol and its Carbon Analogue  | | | Abstract
| In the course of systematic investigations on sila-substituted parasympatholytics the diphenyl(2-aminoethoxymethyl)silanols 3b and 4b (and its carbon analogue 4a) were synthesized and characterized by their physical and chemical properties. In the solid state 4a and 4b form strong 0-H---N hydrogen bonds, which are intramolecular (4a) and intermolecular (4b), respectively. 4 a and 4 b were found to be weak antimuscarinic agents (4b >4a) and strong papaverine-like spasmolytics (4a ^4b). | | |
Reference
| Z. Naturforsch. 38b, 738—746 (1983); eingegangen am 5. Januar 1983 | | |
Published
| 1983 | | |
Keywords
| Sila-Substitution, Crystal and Molecular Structure, Antimuscarinic and Papaverine-Like Activity | | |
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| default:Reihe_B/38/ZNB-1983-38b-0738.pdf | | | Identifier
| ZNB-1983-38b-0738 | | | Volume
| 38 | |
143 | Author
| Werner Winter, Reinhard Merkel, Udo Kunze | Requires cookie* | | Title
| Koordinationschemie funktioneller Phosphorylide, V [1] Die Molekülstrukturen der isomorphen Mangan-und Rheniumbromtricarbonyl- komplexe von 2-Methyl-2-(triphenylphosphonio)dithiopropionat Coordination Chemistry of Functional Phosphorus Ylides, V [1] The Molecular Structures of the Isomorphous Manganese and Rhenium Bromotricarbonyl Complexes of 2-Methyl-2-(triphenylphosphonio)dithiopropionate  | | | Abstract
| The isomorphous crystal structures of the manganese and rhenium bromotricarbonyl complexes 2 a, b have been determined at room temperature (Mn) and at —110 °C (Mn, Re; P2x/c, Z — 4). At room temperature, data collection is accompanied by crystal decomposi-tion, and a cleavage of the PPh3 group is suggested by the results as the primary process. The same initial step is thought to be valid for the photodecomposition in solution. The main structural difference between the free and coordinated betaine ligand 1 is the reduced electrostatic interaction of P and S in the complexed form. Einführung | | |
Reference
| Z. Naturforsch. 38b, 747—751 (1983); eingegangen am 20. März 1983 | | |
Published
| 1983 | | |
Keywords
| Manganese, Rhenium, Betaine Complexes, Dithiocarboxylate Complexes, X-Ray | | |
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| default:Reihe_B/38/ZNB-1983-38b-0747.pdf | | | Identifier
| ZNB-1983-38b-0747 | | | Volume
| 38 | |
144 | Author
| Franz Dallaeker, Peter Kramp, Wim Coerver | Requires cookie* | | Title
| Derivatives of 1.3-Benzdioxoles, 49 [1] Preparation and Reactions of 1.3-Benzdioxole-4.5-quinones  | | | Abstract
| 4,5-Dihydroxy-l,3-benzdioxoles, l,3-Benzdioxole-4,5-quinones Treatment of the subst. 4,5-Dihydroxy-l,3-benzdioxoles (la-lm) with silver(I)-carbonate/Celite resp. tetrachloro-l,2-benzoquinone as dehydrogenation agent yields the l,3-benzdioxol-4,5-quinones (2a-2m). These are darkblue or black coloured compounds with a different stability. | | |
Reference
| Z. Naturforsch. 38b, 752—760 (1983); eingegangen am 13. Dezember 1982 | | |
Published
| 1983 | | |
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| default:Reihe_B/38/ZNB-1983-38b-0752.pdf | | | Identifier
| ZNB-1983-38b-0752 | | | Volume
| 38 | |
146 | Author
| Mohamed Rifaat, Hamza Elmoghayar, Mohamed Kamal, Ahmed Ibrahim, Mahmoud Mohamed, Mahfouz Ramiz, MohamedHilmy Elnagdi | Requires cookie* | | Title
| Activated Nitriles in Heterocyclic Syntheses, I Novel Synthesis of Pyrrolones and l,2,4-Triazol-3-oyl nitriles  | | | Abstract
| Heterocyclic Synthesis, Pyrrolones The behaviour of 4-benzylidene-2-oxazolin-5-one (2) and of 4-phenylazo-2-oxazolin-5-one (3) toward a variety of active methylene reagents is reported. Cleavage of the oxazolin-5-one ring was observed in most cases. A variety of new, otherwise, difficult accessible, azolyl derivatives could be prepared. | | |
Reference
| Z. Naturforsch. 38b, 764—768 (1983); received January 5 1983 | | |
Published
| 1983 | | |
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| default:Reihe_B/38/ZNB-1983-38b-0764.pdf | | | Identifier
| ZNB-1983-38b-0764 | | | Volume
| 38 | |
147 | Author
| Klaus Burger, Stephan Tremmel, Gabriele Trost, Reinhold Simmerl, Dieter Hübl | Requires cookie* | | Title
| Zum Cycloreversionsmechanismus von 3.3-Bis(trifluormethyl)-2.2-dihydro-1.4.2-oxazaphosphol-4-enen [1] Cycloreversion Mechanism of 3,3-Bis(trifluoromethyl)-2,2-dihydro-l,4,2- oxazaphosphol-4-enes [1]  | | | Abstract
| [3 + 2]-Cycloreversion Reactions, Trifluoromethyl Substituted 1,3-Dipoles, [3 + 2]-Cycloaddition Reactions, 5,5-Difluoro-4-trifluoromethyl-2-oxazolines, 5 -Fluoro -4 -trifluoromethyl -oxazoles 2,2,2-Trimethoxy-3,3-bis(trifluoromethyl)-2,2-dihydro-l,4,2-oxazaphosphol-4-enes on thermolysis undergo a 1,3-dipolar cycloreversion reaction with formation of bis(trifluoro-methyl) substituted nitrile ylides. Trapping reactions of the 1,3-dipolar species with a,/3-unsaturated carboxylic acid esters and nitriles are described. 2-Aryl-3-carbethoxy-5,5-bis(trifluoromethyl)-l-pyrrolines obtained undergo an uncatalyzed autoxidation pro-cess to give 2-aryl-3-carbethoxy-3-hydroxy-5,5-bis(trifluoromethyl)-l-pyrrolines. 5,5-Di-fluoro-4-trifluoromethyl-2-oxazolines and 5-fluoro-4-trifluoromethyl-oxazoles formed as by-products indicate that the thermal induced [3+ 2]-cycloreversion reaction of2,2,2-tri-methoxy-3,3-bis(trifluoromethyl)-2,2-dihydro-l,4,2-oxazaphosphol-4-enes is most likely a stepwise process. | | |
Reference
| Z. Naturforsch. 38b, 769—780 (1983); eingegangen am 24. Januar 1983 | | |
Published
| 1983 | | |
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| default:Reihe_B/38/ZNB-1983-38b-0769.pdf | | | Identifier
| ZNB-1983-38b-0769 | | | Volume
| 38 | |
154 | Author
| Fritz Seel, Norbert Klein | Requires cookie* | | Title
| N-Methylcarbamoylphosphate, I. Synthese N-Methylcarbamoyl Phosphates, I. Synthesis  | | | Abstract
| Solutions of mono-and bis-N-methylcarbamoyl phosphates in non-aqueous solvents [e.g. acetonitrile, dimethyl formamide, chloroform) and, surprisingly, even in water are readily obtained by the reaction of methyl isocyanate with the solution of an appropriate mono-or dihydrogenphosphate. The course of the reactions and the limited stability of N-methylcarbamoyl phosphate ions in solutions can be monitored through 31 P NMR measurements. Various types of compounds, including a coordination compound of cobalt could.be isolated in crystalline form: [Et3NH]HX, KHX, NH4HX, Na2X • H20, MgX • 4 H20, CaX • H20, SrX • 2 HaO, BaX • H20, ZnX • 5 H20, CdX • 2 H20, [(NH3)5COX]C104, [EtsNHjY, AgY • MeCN, X = MeNHC(0)0P03, Y = [MeNHC(0) 0]2P02. | | |
Reference
| Z. Naturforsch. 38b, 797—803 (1983); eingegangen am 24. Februar 1983 | | |
Published
| 1983 | | |
Keywords
| N-Methylcarbamoyl Phosphates, Preparation, NMR Spectra | | |
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| default:Reihe_B/38/ZNB-1983-38b-0797.pdf | | | Identifier
| ZNB-1983-38b-0797 | | | Volume
| 38 | |
156 | Author
| Wilhelm Isenberg, NaylaK. Homsy, Jens Anhaus, HerbertW. Roesky, GeorgeM. Sheldrick | Requires cookie* | | Title
| Synthese und Struktur von N2S3C1 + SbCI^ Synthesis and Structure of N2S3C1+ SbCl6~  | | | Abstract
| N2S3C1+ SbClö -was prepared by chlorination of N4S4 • SbCls with elemental chlorine. The crystals are monoclinic, P2i/c, with a = 1492.4(4), b = 1233.6(2), c = 1437.5(4) pm, ß = 91.40(2)°, and R = 0.059 for 3663 observed reflections. There are two independent cations and anions in the asymmetric symmetric unit. The appreciable interionic inter-action results in a high density of q = 2.642 g • cm -3 (calcd). In einer vorausgegangenen Arbeit berichteten wir u.a. über Reaktionen des Chlortrithiadiazylchlorids 1 mit Lewis-Säuren [1], Bei diesen Reaktionen wird im allgemeinen nur das ionogen gebundene Cl sub-stituiert, so daß sich Verbindungen der Formel N2S3C1+ MCI4-(M = AI, Fe) ergeben. Lediglich SbCls reagiert mit 1 unter Substitution beider Cl zu N2S3(SbCle)2. Die Bildung der monosubstituierten Verbindung N2S3C1+ SbCls -2 wurde nicht beob-achtet. Nun gelang uns die Darstellung von 2 durch Chlorierung des Addukts N4S4 • SbCls [2] mit ele-mentarem Chlor. Experimenteller Teil | | |
Reference
| Z. Naturforsch. 38b, 808—810 (1983); eingegangen am 25. März 1983 | | |
Published
| 1983 | | |
Keywords
| Chlorotrithiadiazol, Hexachloroantimonate, Crystal Structure | | |
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| default:Reihe_B/38/ZNB-1983-38b-0808.pdf | | | Identifier
| ZNB-1983-38b-0808 | | | Volume
| 38 | |
157 | Author
| Martin Pfisterer, Günter Nagorsen | Requires cookie* | | Title
| Bindungsverhältnisse und magnetische Eigenschaften ternärer Arsenide ET2As2 Bonding and Magnetic Properties in Ternary Arsenides ET2AS2  | | | Abstract
| The interatomic distances of ternary arsenides ET2AS2 with ThCr2Si2-structure were determined by X-ray powder methods (E = Ca, Sr, Ba; T = Cr, Fe, Co, Ni, Cu). The phases were found to behave according to the Zintl-Klemm-Busmann concept. Magnetic susceptibilities were measured. | | |
Reference
| Z. Naturforsch. 38b, 811—814 (1983); eingegangen am 21. März 1983 | | |
Published
| 1983 | | |
Keywords
| Ternary Arsenides, Crystallographic Data, Magnetic Properties | | |
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| default:Reihe_B/38/ZNB-1983-38b-0811.pdf | | | Identifier
| ZNB-1983-38b-0811 | | | Volume
| 38 | |
158 | Author
| Willy Gombler, RyszardW. Kinas, WojciechJ. Stec | Requires cookie* | | Title
| 31 P-15 N Coupling Constants and 15 N/ 14 N Isotope Effects on 31 P NMR Chemical Shifts of 2-Phenylamino-2-oxo(-thioxo, -selenoxo)- 4-methyl-l,3,2-dioxaphosphorinanes and Related Compounds 31P-15N Coupling Constants, 15 N/ 14 N Isotope Effect, 15 N Chemical Shifts, 1,3,2 -Dioxapho sphorinanes  | | |
Reference
| Z. Naturforsch. 38b, 815—818 (1983); received March 21 1983 | | |
Published
| 1983 | | |
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| default:Reihe_B/38/ZNB-1983-38b-0815.pdf | | | Identifier
| ZNB-1983-38b-0815 | | | Volume
| 38 | |
159 | Author
| Hans Sohr, Günter Hanschmann, Hermann Utschik | Requires cookie* | | Title
| Thermoanalytische, IR-spektroskopische und quantenchemische Untersuchungen an Kristallmodifikationen des Trichlorphons Thermo-analytical, IR-spectroscopical and Quantum-chemical Investigations on Crystal Modifications of Trichlorphone  | | | Abstract
| Several modifications of trichlorphone can be prepared by recrystallizing the raw substance from various solvents under special conditions. One of these modifications is obviously an optical isomer. The different thermo-analytical behavior of the modifications is probably due to the relative content of distinct dimer species. This interpretation is supported by quantum-chemical calculations and by analysis of infrared spectra. Die phosphor-organische Verbindung 2.2.2-Tri-chlor-1 -hydroxyethyl-dimethyl-phosphonat (Tri-chlorphon, Metrifonat) ist ein seit etwa 30 Jahren bekanntes Insektizid [1], das auch als Arzneimittel für die Behandlung von Schistosomiasis eingesetzt wird [2]. Diese im folgenden als Trichlorphon be-zeichnete Substanz hat nach Schräder [3] einen Schmelzpunkt von 356-357 K. In den meisten Fäl-len hegen jedoch die von verschiedenen Autoren angegebenen Schmelzpunkte um 348-351 K. Bei der Reinigung von Trichlorphonproben durch Umkristallisieren stellten wir fest, daß man je nach den gewählten Bedingungen mehrere Kristallfor-men erhält, deren Schmelzpunkte zwischen 343 und 383 K variieren. Über die Erscheinung der Polymorphie beim Tri-chlorphon sind uns aus der Literatur keine Hinweise bekannt. Das Ziel unserer Untersuchungen war es deshalb, mit Hilfe strukturanalytischer Methoden eine Erklärung für die beobachteten Schmelzpunkts-differenzen zu finden. Von den bisher publizierten physikochemischen Eigenschaften der Substanz sind neben den zahl-reichen Schmelzpunkten hauptsächlich die optische Aktivität und die Bimolekularität als Ausgangs-punkt für eine Strukturanalyse von Bedeutung. Brienne und Jacques [4] gelang die präparative Dar-stellung einer optisch aktiven Form (Drehung [a] | | |
Reference
| Z. Naturforsch. 38b, 819—824 (1983); eingegangen am 29. November 1982/11. März 1983 | | |
Published
| 1983 | | |
Keywords
| Differential Thermal Analysis, IR Spectra, Quantum Chemistry, Polymorphism, Trichlorphone | | |
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| default:Reihe_B/38/ZNB-1983-38b-0819.pdf | | | Identifier
| ZNB-1983-38b-0819 | | | Volume
| 38 | |
160 | Author
| Gerhard Klebe, JanW. Bats, Karl Hensen | Requires cookie* | | Title
| Coordinative Interactions in Chelated Complexes of Silicon, Part HI Crystal and Molecular Structure of l-Trichlorosilyl-l,2,3,4-tetrahydro-l,10-phenanthroline  | | | Abstract
| The crystal structure of Ci2HiiN2SiCl3 (monoclinic, P2i/m, Z = 2, with a: 9.284(4), b: 7.226(2), c: 10.832(5) Ä, ß = 115.14(3)°) was refined to R(F) -0.035 from 1228 inde-pendent reflections. A trigonal bipyramidal, pentacoordinate silicon is observed. The chelated complex shows two different Si-N bonds, a coordinative bond (1.984(2) A) be-tween Si and N on the axial position and a Si-N single bond (1.737(3) A, equatorial plane), introduced by chemical reaction. The coordinative bond is 14.2% longer than the Si-N single bond. The lengthening of the coordinative bond in the present case is compared with distances in other extracoordinated silicon compounds. | | |
Reference
| Z. Naturforsch. 38b, 825—829 (1983); received March 23 1983 | | |
Published
| 1983 | | |
Keywords
| Crystal and Molecular Structure, Chelated Pentacoordinated Silicon, Lewis Acid Base Interactions, Coordinative Bonding | | |
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| default:Reihe_B/38/ZNB-1983-38b-0825.pdf | | | Identifier
| ZNB-1983-38b-0825 | | | Volume
| 38 | |
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