bluuebunny/crossref_metadata_2025 huggingface dataset:
Nitrosyl- und Thionitrosylkomplexe des Osmiums: [Os(NO)Cl5]⊖ und [Os(NS)Cl5]⊖ / Nitrosyl- and Thionitrosyl Complexes of Osmium: [Os(NO)Cl5]⊖ and [Os(NS)Cl5]⊖
Authors: Weber Rainer , Dehnicke Kurt
Published: February 2015

Osmium pentachloride reacts with NO forming the complex NO [Os(NO)Cl5], which when treated with (PPh3Me)Cl yields PPh3Me[Os(NO)Cl5] and nitrosyl chloride. The thionitrosyl complex AsPh4[Os(NS)Cl5] is prepared by the reaction of OsCl5 • POCl3 with trithiazyl chloride, followed by the reaction of the resulting complex [Os(NS)Cl4 • POCl3] with AsPh4Cl. The complexes are characterized by their IR spectra
Kristall- und Molekülstrukturen von zwei trans-1.2.4.5-Tetraza-3.6-diphospha-cyclohexan-3.6-disulfiden / Crystal and Molecular Structures of Two trans- 1,2,4,5-Tetraza-3,6-diphospha-cyclohexane-3,6-disulfides
Authors: Dirschl Franz , Nöth Heinrich
Published: February 2015

The crystal and molecular structures of two trans-1,2,4,5-tetraza-diphospha-3,6-cyclohexane- 3,6-disulfides, 2 and 3, have been determined by X-ray diffraction methods. The 3,6-diphenyl- 1,2,4,5-tetramethyl-derivative 2 crystallizes in the monoclinic system, space group C He. Its P2N 4 heterocycle adopts a twist conformation. In contrast, the hexamethyl derivative 3 is triclinic, space group P1̅, and its ring shows chair conformation. Torsion angles in these two compounds and similar ones reveal less interaction between lone pairs of electrons on adjacent N-atoms in the chair conformation but stronger interaction of those bound to phosphorus. It is suggested that the latter interaction is responsible for the larger N -P -N bond angle (107°) as compared to the smaller one (101°) in the P2N4 rings present in twist conformation.
Beiträge zur Chemie des Phosphors, 135 [1]. Synthese und Strukturen neuer polycyclischer Organophosphane PnRm (m < n) / Contributions to the Chemistry of Phosphorus, 135 [1]. Synthesis and Structures of Novel Polycyclic Organophosphanes PnRm (m < n)
Authors: Bäudler Marianne , Arndt Volker
Published: February 2015

The novel polycyclic organophosphanes b-P9R5, P10R6, P10R4, P11R5, and P13R5 (R = Me, Et, i-Pr) have been obtained by reacting RPCl2 with white phosphorus and magnesium or by thermolysing P7R5 (perhaps in the presence of P8R6, P9R5 or (PR)5). A strategy for the enrichment or isolation of polycyclic organophosphanes PnRm (m < n) from complex reaction mixtures is described. The structures of the above mentioned compounds have been unambiguously clarified by 31P NMR spectroscopy or X-ray structure analysis. The results clearly indicate that the corresponding phosphorus hydrides PnNm have the same structures. The general structural principles of polycyclic phosphanes are dicussed.
Carboxydiphenylphosphansulfide / Carboxydiphenyl Phosphane Sulfides
Authors: Hennig Heinz-Werner , Sartori Peter , Steinbrecht Ulrich
Published: February 2015

Carboxydiphcnyl phosphane sulfides (C6H5)2P(S)(OC(O)R) (2) (R = CH3 2a, C2H5 2b, C17H35 2c, (CH3)3C 2d, C6H5 2e) were prepared by reacting silver salts of carboxylic acids AgOC(O)R with (C6H5)2P(S)Cl (Scheme 1) or by treating carboxylic acids with (C6H5)2P(S)Cl in the presence of triethyl amine (Scheme 2) and spectroscopically characterized. Thermal stability and stability against hydrolysis of the mixed anhydrides is unusually high.
Fluoride und Fluorosäuren, VI. Verbindungsbildung und Kristallstrukturen im System Ammoniak—Fluorwasserstoff [1, 2] / Fluorides and Fluoro Acids, VI. Compound Formation and Crystal Structures in the System Ammonia-Hydrogen Fluoride
Authors: Mootz Dietrich , Poll Wolfgang
Published: February 2015

The melting diagram of the quasi-binary system NH3-HF between the limits NH4HF2 and HF was redetermined. The compounds NH3 · 4HF, NH3 · 5HF and NH3 · 8HF with melting points of 26, -14 (dec.) and -95 °C (dec.), respectively, were established as the stable phases. Their crystal structures were determined as those of ammonium hydrogen fluorides NH4[F(HF)4], NH4[F(HF)4] and NH4[HF2(HF)3] · 3HF with extended N-H···F and F-H···F hydrogen bonding.
Phasenbeziehungen im System Schwefel—Chlor sowie Kristallstrukturen von SCl2 und SCl4 [1]. / Phase Relations in the System Sulfur—Chlorine and Crystal Structures of SCl2 and SCl4
Authors: Kniep Rüdiger , Körte Lutz , Mootz Dietrich
Published: February 2015

From new DTA and powder diffraction measurements in the binary system sulfur-chlorine a consistent construction of the melting diagram for the region 50-100 atom-% CI was possible. It contains sulfur chlorides of the elemental ratios 1:1, 1:2, 1:3, and 1:4 as the stable intermediate phases, which melt at -80 °C (congr.), -125 °C (incongr.). -75 °C (incongr.) and -34 °C (congr.), respectively. SCI is S2C12 as characterized by its crystal structure by R. Kniep, L. Korte and D. Mootz, Z. Naturforsch, 38b, 1 (1983). Of SC12 a single crystal was grown by zone melting in a capillary and its structure determined as composed of angular molecules SC12 arranged in bimolecular layers (orthorhombic space group P212121; a = 400.19, b = 918.8, c = 1750.5 pm at -134 °C; Z = 4). With SCl3 a new binary solid of the system is reported of a yet unknown structure. SCl4 from its powder diffraction pattern is made probable as an isotype of α-SeCl4, with tetrameric cubane-like molekules S4Cl16.
Die Kristallstruktur des „Indium-Diiodids“ (InIInIIII4) / The Crystal Structure of “Indium -Diiodide” (InIInIIII4)
Authors: Beck H. P.
Published: February 2015

The crystal structure of InIInIIII4 (Indium-diiodide) has been determined by single crystals X-ray methods. The compound crystallized with a GaCl2-type arrangement in the orthorhombic space group Pnna (lattice constants: a = 842.7(3) pm, b = 1096.5(3) pm, c = 1117.3(3) pm). Coordination polyhedra and bond lengths are discussed in comparison with other In iodides.
Das Infrarotspektrum von matrixisoliertem SFCl / Infrared Spectrum of Matrix Isolated SFCl
Authors: Willner Helge
Published: February 2015

The new compound SFCl was obtained by UV photolysis of FC(O)SCl in rare gas matrix and by UV photolysis of Cl2/SF3SF in the gas phase. Isotopic substitution verifies the molecular identity. Eight frequencies from three isotropic molecules determine the force constants fSF = 4.30 and fscl = 2.90 102N/m.
Reaktionen von Phosphanen MenPH3-n (n = 0—3) mit Hexafluorisopropylidenimin / Reactions of the Phosphanes MenPH3-n (n = 0—3) with Hexafluorisopropylidenimine
Authors: Kischkel Helmut , Röschenthaler Gerd-Volker
Published: February 2015

The insertion of hexafluoroisopropylidenimine (1) into the P - H bonds of the phosphanes PH3, MePH2 and Me2PH yields the (1,1,1-Trifluoro-2-amino-2-trifluoromethyl)ethylphospanes (2-4). Trimethylphosphane is oxidized to give the phosphine-imine Me3P = N-CH(CF3)2 (5).
Synthesis of Regio- and Stereospecifically Deuterium Labelled 2-Benzylindanes
Authors: Kuck Dietmar
Published: February 2015

2-Benzylindenes (1, 1a ) are hydrogenated to 2-benzylindanes (2) using tris-(triphenylphosphine)- rhodium (I)-chloride in benzene by a strict cis-1,2 addition of hydrogen to the double bond. Thus, stereo- and regio-specific deuterium labelling at the five-membered ring of various 2-benzylindanes has been carried out. The high selectivity of deuterium incorporation is shown independently by 1H NMR and mass (MIKE*) spectrometry of selected 2-benzylindanes.
Metall-π-Komplexe von Benzolderivaten, XXI [1]. Bis(η1.2.3.4.4a.9a-anthracen)chrom und Bis(η1.2.3.4.4a.9a-9.10-dihydroanthrancen)- chrom durch Metallatom-Ligand-Cokondensation / Metal-π-Complexes of Benzene Derivatives, XXI [1]. Bis(η1.2.3.4.4a.9a-anthracene)chromium and Bis(η1.2.3.4.4a.9a-9,10-dihydroanthracene)chromium via Metal Atom Ligand Cocondensation
Authors: Elschenbroich Christoph , Möckel Reinhart , Bilger Edgar
Published: February 2015

Cocondensation of chromium atoms with anthracene vapor affords bis(η1.2.3.4.4a.9a-anthracene)- chromium (1) which was characterized as the radical cation 1+̣ in fluid solution by means of ESR spectroscopy. Conspicuous features of this new π-complex are the ease of ligand displacement (τ1/2 ≈ 10 min. THF, 233 K) and the ready hydrogenation in 9,10-position of the ligand which already occurs under mild conditions (e.g. methanol). The product of hydrogenation, bis (η1.2.3.4.4a.9a-9,10-dihydroanthracene)chromium (2) was synthesized independently and studied by 1H, 13C NMR (2) and ESR(2+̣) spectroscopy. A qualitative rationalization is given for the observed trend of increasing lability and propensity to hydrogenation: (η6-biphenyl)2chromium < (η6-phenanthrene)2chromium < (η6-naphthalene)2chromium < (η6-anthracene)2chromium.
Versuche zur Oxidation von 1.5-Benzothiazepin — bzw. 1.5-Benzoxazepin- 2.4-3H.5H-dionen / Investigations Concerning Oxidation Reactions of 1,5-Benzthiazepin — and 1,5-Benzoxazepin- 2,4-3H,5H -diones
Authors: Kollenz G. , Seidler P.
Published: February 2015

Attempts to oxidize the 1,5-benzothiazepin-2,4-3H,5H-dione (1) using NaNO2/Acetic acid lead to isolation of two ring contracted products, namely the 1,4-benzthiazin-derivatives 4 and 5. A reasonable reaction pathway concerning the formation of these compounds is discussed. A simple synthesis of 6-methyI-1,5-benzoxazepin-2,4-3H,5H-dione (13) is described, the transformation of which into the corresponding vic. trione fails, even using a great number of oxidizing procedures. In some cases so far unknown malonic acid derivatives 14, 15 and 16 can be obtained.
Reactions with 5-Arylmethylene-2-phenylhydrazono-4-thiazolidinones A Novel Synthesis of Thiazolo[2,3-c]triazine Derivatives
Authors: Allah Sanaa O. Abd , Fahmy Sherif M. , Ead Hamed A.
Published: February 2015

The 5-arylmethylene derivatives of 2-phenylhydrazono-4-thiazolidinone (1) reacted with phenacyl bromide and with ethyl bromoacetate to yield the thiazolo[2,3-c]triazine derivatives (3) and (4). The reaction of 1 with carbon disulphide in alkaline solution afforded the bis(N1- 2-phenylhydrazono-4-thiazolidinone)thiocarbonyl derivatives (6). Cyanoethylation of 1 afforded the N1-β-cyanoethylphenylhydrazono derivatives (7).
Über eine thermische Transmethylierungsreaktion bei Flavon-5-methylethern / On a Thermal Transmethylation Reaction with Flavon-5-methylethers
Authors: Geiger Hans , Casteele Karel Vande , Sumere Christiaan F. Van
Published: February 2015

Upon heating to 300 °C partial luteolinemethylethers undergo transmethylation. A reaction mechanisme is put foreward.
Bioactive Polymers, XIV. Immobilization of Ampicillin on BIOZAN R
Authors: Simionescu Cr. , Popa M. I. , Dumitriu S.
Published: February 2015

The ampicillin coupling on BIOZAN R (a polysaccharide of microbial synthesis Xanthomonas campestris) is studied by the activation of carboxylic groups by dicyclohexylcarbodiimide. The following optimum reaction parameters are settled on the basis of an experimental program: time = 7.5 h, temperature = 10 °C, dicyclohexylcarbodiimide concentration = 1.10-3 mole, ampicilline concentration = 2.4·10-3 mol. Under these conditions up to 37% of ampicillin with respect to the polymer is coupled.

The microbiological and hydrolysis studies under the conditions of the human physiological pH attest the ampicillin maintains its activity and may be released in oral administration.
Notizen: Gezielte Synthese des Thionylkomplexes Fe3(CO)9S(SO) durch Oxidation einer Sulfidobrücke in Fe3(CO)9S2 / Directed Synthesis of the Thionyl Complex Fe3(CO)9S(SO) by Oxidation of One Sulfido Bridge in Fe3(CO)9S2
Authors: Lorenz Ingo-Peter , Messelhäuser Johannes
Published: February 2015

One of the sulfido bridges in the cluster Fe3(CO)9S2 1 is oxidized by meta-chloroperbenzoic acid to give the known thionyl complex Fe3(CO)9S(SO) 2.
Notizen: Synthese von D-Forosamin aus D-Glucose / Synthesis of D-Forosamine from D-Glucose
Authors: Voelter Wolfgang , Malik Abdul , Afza Nighat
Published: February 2015

A convenient synthesis of the naturally occurring deoxyamino sugar forosamine from glucose as starting material is described. The yields for the intermediates (ethyl-4,6-di-O-toxyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside, 4-iodo-2,3,4-tride-oxy-6-O-tosyl-α-D-threo-hex-2-enopyranoside, ethyl 4-azido-2,3,4-trideoxy-6-O-tosyl-α-D-erythro hex-2-enopyranoside, ethyl 4-amino-2,3,4,6-tetradeoxy-α-D-erythro-hexopyranoside) are all in the range between 70 to 80%.
Die Kristallstruktur des Ethylendiammonium-hexasulfids (2. Mitteilung über Alkylammonium-Polysulfide [1])/The Crystal Structure of Ethylenediammonium Hexasulfide
Authors: Böttcher P. , Buchkremer-Hermanns H. , Baron J.
Published: February 2015

Ethylenediammonium hexasulfide has been synthesized from ethylenediamine, sulfur, and gaseous H2S in aqueous solution. X-ray investigations on single crystals revealed its structure. The monoclinic unit cell contains eight formula units, the space group is Cc. The sulfur atoms form unbranched zig-zag chains S6
2- in all-trans-conformation.
Zur Kenntnis der Hochdruckphase BaAl2/ On BaAl2, a High Pressure Phase
Authors: Cordier Gerhard , Czech Erwin , Schäfer Herbert
Published: February 2015

At 30 kbar and 1000 °C in the Ba/Al-system the compound BaAl2 exists, which remains metastable under standard temperature and pressure after quenching. The new compound crystallizes in the MgCu2-type with a = 870.2(5) pm.
Metalltetrahydridoborate und Tetrahydridoborato-metallate, 12 [1] Zur Kenntnis von Calcium-bis(tetrahydridoborat)-bis(dimethylglykolether)/Metal Tetrahydroborates and Tetrahydroborato Metalates, 12 [1] On Calcium Bis(tetrahydroborate)-bis(dimethylglycolether)
Authors: Hanecker Elisabeth , Moll Josef , Nöth Heinrich
Published: February 2015

Ca(BH4)2·2(CH3OCH2CH2OCH3)2, (1) has been prepared from Ca(BH4)2·2 THF by ligand displacement. IR and NMR data are in agreement with the presence of a nonionic BH4 group, but a specific binding to calcium could not be deduced unambiguously. However, the X-ray structure analysis of a single crystal of 1 reveals that the lattice is built up from molecules of 1 in which each BH4 group binds to Ca via three hydrogen atoms, and the ether forms a chelate. Therefore, calcium in 1 is decacoordinated. Taking the boron atoms as the center of gravity for the BH4 groups one can best describe the coordination as being derived from a strongly distorted octahedron due to repulsive interactions of the BH4 groups as well as of the "bite” of the chelating diether which im poses a O-Ca-O bond angle of ~ 67°.
Beiträge zur Chemie des Phosphors, 139 [1] Triethyl-cyclotriphosphan, Trimethyl-cyclotriphosphan; Gleichgewichte zwischen Cyclophosphanen (PR)n bei erhöhten Temperaturen/Contributions to the Chemistry of Phosphorus, 139 [1] Triethylcyclotriphosphane, Trimethylcyclotriphosphane; Equilibria between Cyclophosphanes (PR)n at Elevated Temperatures
Authors: Baudler Marianne , Hahn Josef , Clef Erwin
Published: February 2015

Triethylcyclotriphosphane, (PEt)3 (1), has been generated by thermolysis of tetraethylcyclotetraphosphane, (PEt)4. 1 can be obtained as a 43% solution in 1,2,3-triethyl-1,2,3-triphosphole, (PEt)3C2H2 (3), by fractional distillation of the product mixture formed in the reaction of K2(PEt)4 with ClHC=CHCl. 3 has been isolated and fully characterized. Furthermore 1 as well as (PMe)3 (2) and (PPh)3 exist besides (PR)4 (R = Et, Me, Ph) in thermodynamic equilibrium with (PR)5 at elevated temperatures; for R = Ph(PPh)6 is also formed. The thermodynamic data of the reactions 3/5 (PMe)5 ⇌ (PMe)3 and 4/5 (PMe)5 ⇌ (PMe)4 have been calculated from the equilibrium constants between 60 and 160 °C. The ring strain of 2 is much smaller than that of cyclopropane but increases with increasing size and bulk of the substituents R at the phosphorus threemembered ring.
Röntgenographische und spektroskopische Untersuchung einiger gemischter Magnesium/Calcium-Fluoroapatite/X-Ray and Spectroscopic Investigation of Some Mixed Magnesium/Calcium Fluoroapatites
Authors: Apella M. C. , Baran E. J.
Published: February 2015

Crystallographic data for mixed apatites of general formula MgxCa10-x(Po4)6F2 (x = 1 - 4) have been obtained from X-ray powder data. The unit cell becomes increasingly distorted with the increase of magnesium concentration. The infrared and Raman spectra show that the magnesium incorporation has a negligible effect on the strength of the P - O bonds. The results are discussed in relation with their relevance to the properties of vertebrate hard tissues.
Structures of 5,10-Dihydro-5,10-dimethylphenaziniumyl (M2P+)-hexafluorophosphate and 5,10-Dihydro-5,10-diethylphenaziniumyl (E2P+)-bromide-dihydrate
Authors: Dietz Karlheinz , Keller Heimo J. , Nöthe Dietrich , Wehe Dieter
Published: February 2015

M2P - PF6 (1) C14H14N2PF6. Mr = 355.25, monoclinic Cc, a = 14.544(3) Å, b = 6.23(1) Å, c = 18.542(4) Å, β = 121.32(2)0, V = 1457.7 Å3, dr = 1.62 Mg · m-3, Z = 4. The M2P+ ion is nearly planar. No overlaps between adjacent M2P+ ions occur. Final refinement gave R = 0.119 and Rw = 0.055, using 1064 unique observed reflections. E2P-Br · 2H2O (2) C16H22N2O2Br, Mr = 354.27, monoclinic C 2/c, a = 21.732(5) Å, b = 5.3464(9) Å, c = 14.436(3) Å, β = 105.01(2)°, V = 1621.19 Å3, dr = 1.45 Mg · m-3, Z = 4. The planar centrosymmetric E2P+ ions form segregated regular stacks along b with interplanar distances of 3.47(3) Å. Every Br- ion is coordinated with two water m olecules. Final refinement yielded R 0.045 and Rw = 0.039 for 1038 reflections with I ≥ 1.5 (I).
Oberflächenverbindungen von Übergangsmetallen, XXVII [1] Lumineszenzerscheinungen an Oberflächenverbindungen des Chroms auf Silicagel/Surface Compounds of Transition Metals, XXVII [1] Luminescence Phenomena of Chromium Surface Compounds on Silicagel Supports
Authors: Morys Peter , Gorges Ulrich , Krauss Hans-Ludwig
Published: February 2015

The red chem iluminescence (CL) of coordinatively unsaturated surface chromium(II) compounds in their reaction with O2 has been studied at various reactivities of the products and various reaction temperatures. With compounds of high reactivity, two CL’s were observed: the first - spectrally unstructured - appears at T ≧ -130 °C, the second - being more intense and spectrally well structure - at T ≧ -90 °C. In course of both these CL’s O2 is released. - Below -130 °C, oxidation takes place without any luminescence. On heating of the reaction product in

vacuo, the luminescence phenomena are observed as a two-stage thermoluminescence (TL).

With the final oxidation product, a photoluminescence (PL) can be stimulated by UV irradiation which is identical with the second CL and shows a well resolved vibrational fine structure at -196 °C. Probably this PL as well as the second CL is produced essentially by an undisturbed monochromate surface species. The first CL and a small part o f the PL is attributed to a topologically broad population of a “disturbed” chromate surface species.

Surface chromium(II) compounds of low reactivity show a one-component CL, TL and PL, almost identical with the first CL mentioned above; they obviously contain the ‘"disturbed” species only.

The mentioned species, defined by their luminescence behaviour, are postulated to be members of the known families of surface chromium occurring in Phillips catalysts, CrA
II and CrB
II, respectively.
Übergangsmetall-Carben-Komplexe, CXXXIII [1] Darstellung, spektroskopische Daten und Molekülstrukturen neuartiger Eisencarben-Komplexe/Transition Metal Carbene Complexes, CXXXIII [1] Preparation, Spectroscopic Data and Molecular Structures of Novel Iron Carbene Complexes
Authors: Fischer Ernst Otto , Schneider Johannes , Ackermann Klaus
Published: February 2015

The reaction of Fe(CO)5 with LiNiPr2 and subsequent treatment with Et3OBF4 results in the formation of (CO)4 Fe[C(NiPr2)OC2H5] (1). As a second product the cyclic carbene complex

(2) is formed.
Rose Bengal and Non-Polar Derivatives: The Birth of Dye Sensitizers for Photooxidation+
Authors: Lamberts Joseph J. M. , Neckers D. C.
Published: February 2015

The synthesis of a new rose bengal derivative, 6-O-acetyl rose bengal ethyl ester is reported. The spectral properties of various new rose bengal derivatives are discussed in relation to their structures and compared with results found for the other fluorescein dyes in the literature. A concise historical review of the chemistry of fluorescein dyes and of their current applications is given.
Studien zum Vorgang der Wasserstoffübertragung, 70 [1] Über den Einfluß der Struktur des Co-Katalysators auf die Hydrierung von Hexen-1 mit Rh(I)-Phosphin-Komplexen. Gibt es einen „Scheibenwischer-Effekt“?/Studies on the Occurrence of Hydrogentransfer, 70 [1] On the Influence of the Structure of the Co-Catalyst upon the Hydrogenation of Hexene-1 with Rh(I)-Phosphine-Complexes. Exists a Wind-Screen-Wiper-Effect?
Authors: Horner L. , Simons G.
Published: February 2015

It is well known, that OMe and NMe2
- substituents in the ortho-position of phenyl groups linked to phosphorus as a center o f chirality induce a high optical activity to derivatives of α-acylaminoacrylic acid in the homogeneous hydrogenation with Rh(I)-Phosphine complexes. The influence of the number, position and the nature of OR-substituents in the aromatic systems of tertiary phosphines upon the rate of the hydrogentransfer to hexene-1 as olefine is investigated and discussed (Tables I to V ). For an explanation of the chemical behaviour of co-catalyst containing o-RO-phenylsubstituents a short lasting coordinative interaction between the oxigen atom of the OR-substituent and the Rh(I) as the central atom is postulated (wind-screen-wipereffect), which stabilizes the configuration of a catalytic active intermediate. Triarylarsines with o-RO-phenyl substituents have a lower catalytic activity, as the corresponding phosphines as co-catalysts (Tables VI to VIII).
Studien zum Vorgang der Wasserstoffübertragung, 71 [1] Tertiäre Phosphine mit ortho-ständigen chelatisierungsfähigen funktionellen Gruppen als Co-Katalysatoren der Homogenhydrierung mit Rh(I)-Komplexen/Studies on the Occurrence of Hydrogen Transfer, 71 [1] Tertiary Phosphines with Functional Groups in the ortho-Position Capable for Chelatization as Co-Catalysts of the Homogeneous Hydrogenation with Rh(I)-Complexes
Authors: Horner Leopold , Simons Guido
Published: February 2015

By systematic variation of the structure of tertiary phosphines with ortho-phenyl substituted groups as co-catalysts of the homogeneous hydrogenation with Rhodium complexes and hexene-1 as a model compound a collection of data is obtained. By investigating the influence of the variation of the Rhodium/Phosphine-Ratio (Rh/P) (1:1,1 and 1:2,2) on the rate of the hydrogentransfer indirect conclusion can be drawn on the composition of the complexes in the equilibria responsible for the hydrogen transfer.

Results:

1. Steric effects of substituents linked to the ortho-position of a phenyl group in the co-catalyst are very important (compare the Tables I-V especially Table VI).

2. The rate of hydrogenation is strongly influenced by tertiary phosphines with substituents in a ortho-phenyl group capable for coordination like NR2 and SR. With Rh/P = 1:1,1 the rate of the hydrogenation of hexene-1 is mostly faster as with Rh/P = 1:2,2. Depending on steric effects the rate data can be invers.

3. Tertiary arsines with o-dialkylaminophenyl groups are more effective co-catalyst as the corresponding phosphines (Table V).

4. Tertiary phosphines with an ortho-alkylmercaptophenyl group (38-41) are weakly active cocatalysts using Rh/P = 1:1,1.

The thioether 42 (in compounds 12 the diphenylphosphino group is exchanged by the methylmercapto group) is also a moderate active co-catalyst.

5. As a conclusion: it is assumed that complexes of the structure A can coordinate with the substrates hydrogen and olefine . Complexes of the structure B seen to be to stable for the activation of the substrates.
Studien zum Vorgang der Wasserstoffübertragung, 72 [1] Versuche zur enantioselektiven Homogenhydrierung von N-Acyl-α-aminozimtsäuren mit Rh(I)-Komplexen unter Verwendung neuer optisch aktiver Co-Katalysatoren/Studies on the Occurrence of Hydrogen Transfer, 72, [1] Investigation on the Enantioselective Homogeneous Hydrogenation of N-Acyl-α-aminocinnamic Acids with Rh(I)-Complexes Using New Optically Active Co-Catalysts
Authors: Horner L. , Simons G.
Published: February 2015

3 Optically active compounds of the type I and 15 optically active compounds of the type II were investigated as co-catalysts in the homogeneous hydrogenation of N-acyl-α-aminocinnamic acids using standard conditions. In the co-catalysts of the type I the phosphorus atom is the center of the asymmetry. In the representatives of type II the side chain is optically active and the three bonded phosphorus either achiral or optically active.

The results of the homogeneous hydrogenation are deposited in the Tables I-IV. In the Tables I and IV the degree of the optical induction and the configuration of the excess enantiomer are determined using Rh/P-ratios 1:1,1 and 1:2,2. The Tables II and III show the results applying a Rh/P-ratio of 1:2,2. The observed degree of optical induction is low with the co-catalysts 1-18; only the co-catalyst 19 shows an optical induction of 68%.

A change of the configuration of the excess enantiomer of N-benzoylphenylalanine formed by the homogeneous hydrogenation of N-benzoyl-α-cinnamic acid for the first time was observed by varying the Rh/P-ratio of the co-catalysts 14, 17 and 18 from 1:1,1 to 1:2,2.
Über Synthesen unsymmetrisch substituierter Bis(phenyI)bis(triphenylphosphan)pIatin(II)-Verbindungen mit ortho-ständigen Substituenten/Syntheses of Unsymmetrically Substituted Bis(phenyl)bis(triphenylphosphane)platinum (II) Compounds with ortho-Substituents
Authors: Brune Hans Albert , Schmidtberg Günther , Wiege Manfred
Published: February 2015

The influence of ortho-substituents on the formation of cis- and trans-Bis(phenyl)bis(triphenylphosphane) platinum (II) compounds has been tested; 12 new compounds of this type were synthesized.
Notizen: Die Kristallstruktur von AuBr · S(CH2C6H5)2 und AuCl · S(CH2C6H5)2/The Crystal Structure of AuBr · S(CH2C6H5)2 and AuCl · S(CH2C6H5)2
Authors: Strähle Joachim , Hiller Wolfgang , Conzelmann Walter
Published: February 2015

Bromo(dibenzylsulfide)gold(I) and chloro(dibenzylsulfide) gold(I) crystallize isotypic with four formula units AuX · S(CH2C6H5)2 in the tetragonal space group P41. The lattice constants are a = 1056.7(2), c = 1286.3(3) pm (X = Br) and a = 1046.2(3), c = 1288.5(6) pm (X = Cl), respectively. The structures consist of individual complexes in which each gold atom has a linear coordination of one halogen atom and the S atom of the Lewis base. These complexes are arranged along the screw axis 41, forming an almost linear Au-Au chain with distances of 329 pm (X = Br) or 330 pm (X = Cl).
Notizen: Synthese strukturisomerer Dihydroxiderivate von Dibenzo-18-krone-6/Synthesis of Isomeric Dihydroxy Derivatives of Dibenzo-18-crown-6
Authors: Rieckemann Bernd , Ebhardt Klaus-B. , Umland Fritz
Published: February 2015

In 1967 Pedersen described dibenzo-18-crown-6 (1) [1]. We report the preparation of its isomeric dihydroxy derivatives 2c and 3c. Nitration of 1 in acetic acid and chloroform yields the dinitro compounds 2a and 3a. 2a and 3a have different solubility in ethylene glycol monomethyl ether and can be separated [4]. Catalytic reduction of the dinitro derivatives with hydrazine and Raney nickel leads to the diamines 2b and 3b. The diazonium salts of 2b and 3 b are heated in dilute sulfuric acid and yield the phenols 2c and 3c.
Metallaustausch an Clustern unter Redox-Bedingungen / Metal Exchange in Clusters under Redox Conditions
Authors: Honrath Ute , Vahrenkamp Heinrich
Published: February 2015

The paramagnetic clusters ECo3(CO)9 with E = S, Se, P-t-Bu. PPh, PNEt2, POBu, PSEt, some of which were fully characterized for the first time, were reacted with Na2Fe(CO)4. The resulting metal exchange which is a redox reaction with formation of NaCo(CO)4 produced the clusters EFeCo2(CO)9. Further treatment with Na2Fe(CO)4 and acidification produced the clusters EFe2Co(CO)9H, the anions of which could be isolated as PPN salts. Electron transfer catalysis with benzophenone ketyl allowed the conversion of EFeCo2(CO)9 (E = S, Se, PNEt2) with NaMCp(CO)3 (M = Mo, W) into the chiral clusters EFeCoM(CO)8Cp
Die Kristallstruktur des α-Na2S5 / The Crystal Structure of α-Na2S5
Authors: Böttcher P. , Keller R.
Published: February 2015

Na2S5 has been Synthesized from β-Na2S2 and excess sulfur by a two step reaction. A solid state reaction at 200 °C was carried out, which was then followed by a melting reaction at 500 °C. X-ray investigations on single crystals revealed the structure of the α-modification. The orthorhombic unit cell contains four formula units; the space group is Pnma. The sulfur atoms form unbranched zig-zag-chains S5
2- in cis-conformation
Crystal Structure of 2-Thiopyrrole-1,2-dicarboximide-(bis-triphenylphosphine)copper(I)chloride, [(Ph3P)2Cu(Cl)C6H4N2OS]
Authors: Pandey Krishna K. , Noltemeyer Mathias , Sheldrick George M. , Saheb Ray
Published: February 2015

Crystals of the title compound are monoclinic, space group C2/c, a = 3858.0(7), b = 1013.8(2), c = 2982.1(6) pm, β = 139.76(3)° and Z = 8. The structure was refined to R = 0.063 for 2155 unique observed diffractometer data. The copper atom is coordinated tetrahedrally by 2P, CI and S, contrary to a previous spectroscopic assignment
Vergleichende Untersuchungen an Pb8Tl5O24-, α-PbO2- und Tl2O3-Elektroden / Comparative Investigations of Pb8Tl5O24, α-PbO2 and Tl2O3 Electrodes
Authors: Tillmetz Werner , Wabner Dietrich
Published: February 2015

The anodic deposition of Pb8Tl5O24 is compared with that one of Tl2O3 and α-PbO2. Scanning electron microscopic pictures of the oxide surfaces show obvious differences. This should be the reason for different oxygen overpotentials measured at these anodes. Comparative cyclic voltammograms show, that the redox behaviour of Pb8Tl5O24 in sulfuric acid is essentially determined by the lead ions. Because of the high corrosion rate Pb8Tl5O24 is not suitable as anode material for electrolysis in sulfuric acid
Synthese und Struktur einiger Methyl(dicarboxilato)stibane / Syntheses and Structure of Some Methyl(dicarboxilato)stibanes
Authors: Wieber Markus , Wirth Dieter , Burschka Christian
Published: February 2015

Methyldiethoxistibane and maleic or phthalic acid in a ratio of 1:1 in ethanolic solution at -78 °C react to give methyl(maleato)stibane (1) and methyl(phthalato)stibane (2) respectively. At room temperature polymeric compounds of the same analytical composition are obtained (1a and 2a).

The crystal structure of the solid methyl(phthalato)stibane 2 was determined by X-ray diffraction. It shows that the central antimony atom is hexacoordinated by addition of a solvate ethanol. The correct formula for the solid should be
Acetylacetonatobis(cyclopentadienyl)titanium(IV) and -zirconium(IV) Dithiocarbamates
Authors: Sharma Anand K. , Kaushik N. K.
Published: February 2015

A series of acetylacetonatobis(cyclopentadienyl)titanium(IV) and zirconium IV) dithiocarbamates of the type [Cp2M(acac)]+ dtc- (M = Ti or Zr, Hacac = acetylacetone, dtc- = Me2NCS2
-
, Et2NCS2
-
, i-Pr2NCS2
-, Me, cyhxNCS2
-, Et, cynhxNCS2
- and i-Pr, cyhxNCS2
-) have been synthesised by the reaction of [Cp2M(acac)]+CI- with Nadtc in aqueous medium. The compounds have been characterised on the basis of chemical analysis, conductance, IR and 1H NMR spectral studies
Molecular Structures of p-Methylsulphonylbenzoic Acid and Methylphenylsulphone: Comparison of X-Ray and Electron Diffraction Results
Authors: Brunvoll Jon , Colapietro Marcello , Domenicano Aldo , Marciante Clara , Portalone Gustavo , Hargittai István
Published: February 2015

The molecular structures of p-methylsulphonylbenzoic acid and methylphenylsulphone have been accurately determined by X-ray crystallography and gas electron diffraction, respectively. After correction for systematic effects, the geometry of the crystal molecule is seen to agree with that of the free molecule within a few thousandths of an Å unit for bond distances and a few tenths of a degree for bond angles. An exception is the S-Me bond distance, which is ca. 0.02 Å shorter in the crystal. The distortion of the benzene ring angles from 120°, an effect of the - SO2Me substituent, is virtually the same from both experiments
Ein- und Zweielektronen-Oxidation von Phosphor-Yliden mit Kupfer(II)-Salzen / One- and Twoelectron Oxidation of Phosphorus Ylides Using Copper(II) Salts
Authors: Bowmaker Graham A. , Dörzbach Cornelia , Schmidbaur Hubert
Published: February 2015

The reaction of CuCl2 with equimolar quantities of an ylide R3P=CH2 (1a-c, R=CH3, C2H5, C6H5) in anhydrous tetrahydrofuran at low temperature leads to oxidative coupling, with ethylidene-1,2-bis-phosphonium salts R3P⊕-CH2-CH2-P⊕R3 2X⊖ (2, 3a-c) as high- yield products. The process is interpreted as a one-electron transfer to give radical cations R3P⊕-ĊH2 (II) which subsequently undergo dimerization. The initial counterions CuCl2
⊖ (in 2a-c) can be replaced by PF6
⊖ (as in 3a-c). (C2H5)3P=CHCH3 (1d) yields the cation (C2H5)3P⊕-*CH(CH3)-*CH(CH3)P⊕(C2H5)3 with two chiral centers as a mixture of diasteromers RR/SS, RS. The ratio of the components is 2,8:1. as evaluated by NMR spectroscopy.

The analogous reaction with (C6H5)3P=CHCH3 and (C6H5)3P=C(CH3)2 (1e, f) takes a very different course. Along with minor quantities of (C6H5)3P⊕CH2CH3/(C6H5)3P⊕CH(CH3)2 species, mainly 1-chloroalkyl-phosphonium cations are formed, which were again isolated as the hexafluorophosphates (4a, 4b: [(C6H5)3P⊕CH(CI)CH3]PF6
⊕, [(C6H5)3P⊕C(Cl)(CH3)2]Pf6
⊖). H-radical trapping from the medium by II ist proposed for the formation of the former, while a two- electron oxidation followed by addition of Cl⊖ is the most plausible mechanism for the generation of the latter
Die wahrscheinliche Struktur des gelben Natriumpolymolybdats / The Probable Structure of the Yellow Sodium Polymolybdate
Authors: Richter Horst , Fuchs Joachim
Published: February 2015

Na2Mo4O13 · 6H2O obtainable by the acidification of sodium molybdate solutions crystallizes as needles which are constituted of tiny fibers. Under mild hydrothermal conditions crystal needles can be obtained in which the fibers exhibit a certain order so that a rough structure determination could be carried out by the single crystal method and the molybdenum positions ascertained. The compound crystallizes in the space group P21 with the lattice constants a = 21,202 Å, b = 10,160 Å, c = 7,81 Å, β = 100,1°. It contains chain-like anions which are evidently made up from Mo8O28 units. The concatenation of there moieties is a novel feature
Polyine, IV [1]. Synthese unsymmetrisch-substituierter Diacetylene über 1.1.2-Trichlor-1-alken-3-ine / Polyynes, IV [1]. Synthesis of Unsymmetrically Substituted Diacetylenes via 1,1,2-Trichloro-1-alken-3-ynes
Authors: Himbert Gerhard , Umbach Hermann , Barz Michael
Published: February 2015

Phenylacetylene (1a ) and 1-hexyne (1b ) react with bromo(ethyl)magnesium and trichloroacetaldehyde to the corresponding acetylenic carbinols 2. Successive treatment of 2 with phosphorus pentachloride and triethylamine furnishes via the 1,1,1,2-tetrachloro-3-alkynes 3 the trichlorovinylacetylenes 5. The butyl derivatives 3b and 5b are accompanied by the allene 4b, formed by propargyl rearrangement and not attacked by triethylamine. The trichlorovinyl compounds 5 (and the tetrachloroallene 4 b) react with butyllithium to the corresponding lithium butadiynides 6, which can be transformed into the disubstituted 1,3-butadiynes 7 by the reaction with electrophilic substances. The applicability, the variability and the easiness of this procedure is explained and compared with other methods used for preparing disubstituted diacetylenes
Übergangsmetall-Carben-Komplexe, CXXXIV [1]. Synthese neuer Mono- und Biscarben-Komplexe der VI. Nebengruppe; Röntgenstruktur des ersten Bis[amino(alkoxy)carben]-Komplexes / Transition Metal Carbene Complexes, CXXXIV [1]. Synthesis of New Mono- and Bis-Carbene Complexes of Group VIb Elements; Structure of the First Bis[amino(alkoxy)carbene]-Complex
Authors: Fischer Ernst Otto , Reitmeier Rudolf , Ackermann Klaus
Published: February 2015

The hexacarbonyl compounds of chromium, molybdenum and tungsten react with the highly nucleophilic agent Li NiPr2 and in a subsequent alkylation with (Et3O)BF4 to give the carbene complexes (CO)5M[C(N′Pr2)OEt] (1, 3, 4). In case of W(CO)6 and Mo(CO)6 the novel biscarbene complexes cis(CO)4M[C(NiPr2)OEt]2 (2, 5) are additionally obtained. Reaction conditions, properties and spectroscopic data of the new compounds are reported. The molecular structure of cis(CO)4W[C(NiPr2)OEt]2 (4) was determined by X-ray crystallography
Functionalized 1,2-Dioxetanes as Potentially Useful Biological and Chemotherapeutic Agents
Authors: Adam Waldemar , Babatsikos Chrisostomos , Cilento Giuseppe
Published: February 2015

Hydroxymethyl-substituted 1,2-dioxetanes (3) have been converted in reasonable yields (10-40%) into the carboxylate-substituted 1,2-dioxetanes (4) by means of the Brewster-Ciotti or Mitsunobu esterification and into the tosylate-substituted 1,2-dioxetanes (5) by means of tosyl chloride in pyridine. The fact that hydroxy-functionalized 1,2-dioxetane can be chemically attached to carboxylic acids and sulfonic acids whit preservation of the dioxetane moiety opens up new opportunities for biomedical applications
Isolation, Structure and Oxidative Fragmentation of 16-epi-19-S-Vindolinine – an Alkaloid from the Leaves of Catharanthus roseus
Authors: Rahman Atta-ur , Bashir M. , Kaleem S. , Fatima T.
Published: February 2015

A new alkaloid has been isolated from the leaves of Catharanthus roseus. Spectroscopic and degradative studies have established its structure to be 16-epi-19-S-vindolinine
Darstellung und Kristallstruktur von Tl4TiS4, TI4SnS4 und Tl4TiSe4 / Preparation and Crystal Structure of Tl4TiS4, TI4SnS4 and Tl4TiSe4
Authors: Klepp Kurt O. , Eulenberger Günther
Published: February 2015

The isostructural compounds Tl4TiS4, Tl4SnS4 and Tl4TiSe4 crystallize in the monoclinic system, space group P21/c with a = 8.328, b = 8.191, c = 15.248 Å, β = 104.53°; a = 8.395, b = 8.280, c = 15.398 A, ft = 103.69°, and a = 8.517, b = 8.389, c = 15.672 Å, β = 103.50°, respectively. There are four formula units in the unit cell. The crystal structures were determined and refined from single crystal diffractometer data. They are characterized by isolated tetrahedral thioanions which are connected with each other by Tl+ ions. The mean bond lengths are Ti-S = 2.26 Å, Sn-S = 2.40 Å and Ti -Se = 2.38 Å. The Tl atoms are surrounded by six and seven chalcogen atoms, respectively, in an irregular and polar arrangement, thus indicating stereochemical activity of the lone electron pair of the Tl+ ions. Tl-S distances vary from 2.93 to 3.98 Å, Tl-Se distances from 3.03 to 3.96 Å. The Tl atoms have nearest Tl neighbours at distances ranging from 3.46 to 3.65 Å. The crystal structure can be described as built from pseudotetragonal slabs oriented parallel to (001) which contain the cations and the tetrahedral anions. It is shown that a similar description is valid also for the crystal structures of Tl4GeS4 [1] and Na4SnS4 [2, 3].
Der ThCr2Si2-Typ und verwandte Strukturen bei APd2X2- Verbindungen (A = Ca, Sr, Ba; X = P, As) / The The ThCr2Si2-Type and Related Structures of APd2X2-Compounds (A — Ca, Sr, Ba; X = P, As)
Authors: Mewis Albrecht
Published: February 2015

The compounds APd2X2 (A = Ca, Sr; X = P, As) have been prepared and their structures have been determined. They are isotypic and crystallize in the ThCr2Si2-type structure with the following lattice constants:

CaPd2P2 a = 414.5(1) pm, c = 965.9(2) pm;

CaPd2As2 a = 429.9(1) pm, c = 1010.2(2) pm;

SrPd2P2 a = 424.1(1) pm, c = 972.4(2) pm;

SrPd2As2 a = 438.3(1) pm, c = 1017.9(2) pm.

Tetragonal symmetry was also found for BaPd2P2 (a = 425,6 pm; c = 564.7 pm) and BaPd2As2 (a = 434.6 pm; c = 575.8 pm ), but these materials crystallize in a CeMg2Si2-type structure, whereas the lattice of some selected single crystals of BaPd2As2 have tetragonal symmetry (a = 448.7 pm; c = 2063.5 pm) and show structural elements of CaBe2Ge2 - like those of the CeMg2Si2-type structure.
Synthese und Kristallstruktur von Re(NBCl3)Cl2[P(CH3)2C6H5]3, ein Komplex mit einer Nitridobrücke zwischen Rhenium und Bor / Synthesis and Crystal Structure of Re(NBCl3)Cl2[P(CH3)2C6H5]3, a Complex with a Nitrido Bridge between Rhenium and Boron
Authors: Dantona Robert , Schweda Eberhard , Strähle Joachim
Published: February 2015

ReNCl2(PMe2Ph)3 reacts as a Lewis base and with BCl3 forms a nitrido bridge between Re and B. The resulting complex Re(NBCl3)Cl2(PMe2Ph)3 crystallizes orthorhombic in the space group Pn21 a with Z = 4. In the complex each Re atom has six nearest neighbours in an almost octahedral arrangement with the NBCl3 group being trans to one of the Cl ligands. The difference between the two Re-Cl bond lengths (239,4 and 243,9 pm) indicates a weak trans effect of NBCl3. The linear bridge Re≡N-B has bonding distances of Re-N = 172,8 and N-B = 153 pm. Bonding of BCl3 by the nitrido ligand causes a small increase in the Re-N bond distance.
K2SiP2, ein Phosphidopolysilikat(IV) / K2SiP2, a Phosphidopolysilicate (IV)
Authors: Eisenmann Brigitte , Somer Mehmet
Published: February 2015

The new compound K2SiP2 crystallizes in the orthorhombic system , space group Ibam. The unit cell with the lattice constants

a = 1292.6(6) pm, b - 686.7(4) pm, c - 610.7(4) pm

contains 4 formula units. In the structure SiP4 tetrahedra form chains by sharing common edges. The [(SiP2)2-] strings are isosteric to the SiS2 molecules.
Lichtabsorption von oxidischen Silber(I)-Verbindungen / Light Absorption of Silver(I)-oxides
Authors: Friebel Claus , Jansen Martin
Published: February 2015

Diffuse reflectance spectra of Ag2SO4, Ag3PO4, Ag2CO3, Ag2Ge2O5, AgBO2, Ag3BO3-II, Ag6Si2O7, Ag10Si4O13 and Ag10Ge4O13 in the region ν̄ = 10000-40000 cm-1 and generally at 298 K and ambient pressure were measured. Additional spectra were recorded at 5 K for Ag3BO3 and Ag3PO4, and under application of a static pressure of 80 kbar for Ag10Si4O13. As a common feature all spectra show a steep absorption edge, which is only structured in singular cases. The edges appear in the remarkably wide range from 33100 cm-1 (Ag2SO4) to 13500 cm-1 (Ag10Ge4O13). As the shifts correlate with the dimensions of the cluster-like silver partial structures, the absorptions have been attributed to 4d→5s band-band transitions, an interpretation, which is in agreement with the low temperature and high pressure spectra. However, effects originating from charge-transfer transitions cannot be absolutely excluded.
Darstellung von einigen Phenyldicarboxylatostibanen / Syntheses of Some Phenyldicarboxylatostibanes
Authors: Wieber Markus , Fetzer-Kremling Isa
Published: February 2015

Some phenyldicarboxylatostibanes of the general formula

were synthesized by simple metathesis reactions from phenyldiethoxystibane and carboxylic acids in the ratio 1:2. By reaction of 1,2-dicarboxylic acids with phenyldiethoxystibane in the ratio 1:1 phenyldicarboxylatostibanes are also obtained. Some properties and the 1H NMR spectra of these compounds are described, IR data are reported and discussed.
Radikalionen, 61 [1, 2]Dialkylamino-substituierte Acetylene und Allene:Ionisation, Oxidation und AlCl3-katalysierte Wasserstoffübertragung / Radical Ions, 61 [1, 2]Dialkylamino-substituted Acetylenes and Allenes:Ionisation, Oxidation and AlCl3-Catalyzed Hydrogen Transfer
Authors: Bock Hans , Kaim Wolfgang , Kira Mitsuo , Réné Louis , Viehe Heinz-Günther
Published: February 2015

The photoelectron (PE) spectra of bis(dialkylamino) acetylenes R2N-C≡C-NR2 and of tetrakis(dialkylamino) allenes (R2N)2C=C=C(NR2)2 with R = CH3, C2H5 exhibit characteristic ionization patterns which are assigned to π radical cation states of the two molecular halves twisted against each other. The low first ionization potentials between 7.0 eV and 7.7 eV stimu­lated attempts to oxidize using AlCl3 in H2CCl2 or D2CCl2. The hyperfine structured ESR spectra observed can be unequivocally assigned to the ethylene radical cations R2N-HC=CH -NR2˙⊕ which are formed from the obviously non-persistent species R2N-C≡C-NR2˙⊕ via a hydrogen transfer. During the oxidation of the dialkylamino-substituted allenes no paramagnetic intermedi­ates could be detected, presumably due to a rapid dimerisation of the allene radical cation (R2N)2C=C=C(NR2)2˙⊕.
Radikalionen, 62 [ 1—3]Bis(dimethyIamino)dibenzoheptafulven-Radikalkation /Radical Ions, 62 [1—3]Bis(dimethylamino)dibenzoheptafulvene Radical Cation
Authors: Bock Hans , Roth Bernhard , Daub Jörg
Published: February 2015

The neutral title compound, 8,8-bis(dimethylamino)dibenzo-[a,d]-heptafulvene, exhibits a first vertical ionization potential of only 6.98 eV and, therefore, can also be oxidized by AlCl3 in H2CCl2 solution. The radical cation generated shows a complex multiplet signal pattern, which is assigned based on additional ENDOR measurements. The photoelectron (PE) and ESR spectra of the 112 valence electron molecule are interpreted by “pararneter-optimized” HMO and by geometry-optimized MNDO calculations, which both suggest a non-planar π-type ground state with most of the charge and the spin distributed over the dibenzoheptatriene part of the radical cation.
Zur Reaktion von Hexamethyldistannoxan und Hexamethyldistannthian mit Phosphor-oxo- bzw. -thio-halogeniden. Schwingungsspektren von (Me2PS)2O und (Me2PS)2S / On the Reactions of Hexamethyldistannoxane and Hexamethyldistannthiane with Phosphorus-oxy and -thio-halides. Vibrational Spectra of (Me2PS)2O and (Me2PS)2S
Authors: Shihada Abdel-Fattah , Jasim Ihsan A. M.
Published: February 2015

Me3SnO2PCl2 and (Me2PS)2O are prepared from the reactions of (Me3Sn)2O with POCl3 (1:1) and with Me2PSCl (1:2), respectively. The reactions of (Me3Sn)2S with Me2PSCl and with PSBr3 lead to the formation of (Me2PS)2S and P4S9, respectively. POCl3 reacts with (Me3Sn)2S to give unidentified products as a result of O/S exchange. The i.r. and Raman spectra of the solids (Me2PS)2O and (Me2PS)2S and the Raman spectra of the molten compounds are reported and the frequencies assigned.
Graphite Intercalation Compounds with Trimethyltin Chloride
Authors: Schlögl Robert , Boehm Hanns-Peter
Published: February 2015

Intercalation compounds of graphite with Sn(CH3)3Cl have been prepared by UV irradiation, in the presence of graphite, of solutions of Sn(CH3)3Cl, Sn(CH3)4, or of Sn(CH3)4 + SnCl4 in CCl4. Mixtures of stage 1, stage 2, and stage 3 compounds have been obtained. They were characterized by X-ray diffraction, 119Sn Mossbauer spectroscopy, and by chemical analysis. Apparently an oligomeric, anionic species is intercalated together with some solvent.
Synthese und Eigenschaften von TrimethyIstannylmethyl-Indium(III)-Verbindungen / Preparation and Properties of Trimethylstannylmethyl Indium(III) Compounds
Authors: Schumann Herbert , Mohtachemi Reza
Published: February 2015

Trimethyltin methyllithium reacts with InCl3, CH3InCl2 and R2InCl (R = CH3, t-C4H9) with formation of the new compounds In(CH2SnMe3)3, CH3In(CH2SnMe3)2, (CH3)2InCH2SnMe3 and (t-C4H9)2InCH2SnMe3. The compounds are characterized by elemental analyses, 1H, 13C, 119Sn NMR and IR spectra.
Elektrochemische Synthesen, IX [1]Darstellung CO-freier Metallkomplexe / Electrochemical Synthesis, IX [1] Preparation of CO Free Metal Complexes
Authors: Joseph Grobe , Zimmermann Heinz
Published: February 2015

The electrochemical synthesis of metal acetylacetonates (M = Cr, Mo, V, Ti) from metal anodes and acetylacetone is reported. In the presence of oxygen the oxo compounds OM(acac)2 are formed for M = Mo, V and Ti instead of M(acac)3. The electrochemical production of| Ni(PPh3)4 and Fe(PMe3)4 starting from Ni(acac)2 and Fe metal, respectively, has been investi­gated. Successful carbonylation to Ni(CO)n(PPh3)4-n (n = 1,2) or Fe(CO)m(PMe3)5-m (m = 2, 3) proves the hypothesis that replacement of PR3 ligands by CO takes place after reduction of the central metal to the oxidation state 0.