bluuebunny/crossref_metadata_2025 huggingface dataset:
Gold(I)-Bis(diphenylphosphino)amid und einige Gold(I)-Bis(diarylphosphino)methanide mit sterisch anspruchsvollen Arylsubstituenten / Gold(I)-bis(diphenylphosphino)amide and Some Gold(I)-bis(diarylphosphino)methanides with Bulkyl Aryl Substituents
Authors: Schmidbaur Hubert , Schnatterer Stefan , Dash Kailash C. , Aly Aref A. M.
Published: February 2015

Intensely yellow coloured, insoluble gold(I)-bis(diarylphosphino)amides, [(C6H5)P2NAu, 1, is obtained from lithiated bis(diphenylphosphino)amine and AuCl complexes of tertiary phosphines. 1 is assigned a dimeric eightmembered ring structure on the basis of its 197Au-Mößbauer spectrum and of a direct analogy with the corresponding bis(phosphino)methanide complexes, whose structure has recently been confirmed by X-ray diffraction.

A series of mono- and binuclear AuCl complexes of bis(diarylphosphino)methanes bearing bulky 2-tolyl or 2,6-dimethylphenyl substituents (3a, b) was synthesized from the diphosphines and (CO)AuCl in the molar ratios 1:2 or 1:1. The compounds have structures 4 a, b and oa, b, respectively. An ionic tetrafluoroborate derivative 6 b was obtained from the chloride 5 b on treatment with AgBF4. Lithiation of the diphosphinomethanes 3 a, b using LiCH3 followed by reaction with CIAuPR3 complexes yields the deep-yellow Au(I) bis(diarylphosphino)methanides 7 a, b. All compounds, including the new ligand 3b and its precursor (2,6-(CH3)2C6H3)2PBr, 2, were characterized by analytical and spectroscopic data.
Übergangsmetallketen-Verbindungen, XII [1] Darstellung und Struktur von η5-C5H5(CO)2 [P(CH3)3]W-C≡C-C3H5 / Compounds of Transition Metal Ketenes, XII [1] Synthesis and Structure of η5-C5H5(CO)2 [P(CH3)3]W-C≡C-C3H5
Authors: Sieber Werner , Wolfgruber Mathias , Neugebauer Dietmar , Orama Olli , Kreißl Fritz R.
Published: February 2015

Dicarbonyl(η5-cyclopentadienyl)(η1 -cyclopropylketenyl)(trimethylphosphane)tungsten reacts with carbon monoxide under reduction of the ketene moiety forming a (σ-bonded acetylene compound. Reaction conditions, spectroscopic data and the X-ray structure of the new compound are reported.
Oxamidoximkomplexe des Kupfers: Monomeres Chloro(oxamidoximato)(oxamidoxim)kupfer(II) und polymeres Dichloro(oxamidoxim)kupfer(II). Strukturen und EPR spektroskopische Eigenschaften / Oxamide Oxime Complexes of Copper(II): Monomeric Chloro(oxamidoximato)(oxamidoxim)copper(II) and Polymerie Dichloro(oxamidoxim)copper(II). Structures and EPR Spectroscopic Properties
Authors: Endres Helmut , Gene Nihat , Nöthe Dietrich
Published: February 2015

CU(C2H6N4O2)(C2H5N4O2)Cl (1) crystallizes in the monoclinic space group P21/c, a = 8.191(4), b = 10.746(3), c = 13.340(7) Å, β = 104.94(4)°, V = 1134.5 A 3 , Z = 4, dc = 1.96 gem -3 , final Rw = 0.029 for 1785 reflections. In the monomeric complex molecules Cu is coordinated in the shape of a square pyramid with Cl at the apex. In the basal plane only one intramolecular H bridge exists. Cu(C2HeN4O2)Cl2 (2), crystallizes in the monoclinic space group Pc, a = 7.708(7), b = 3.751(1), c= 13.377(12) Å, β = 105.97(4)°, V = 371.8 Å3 , Z = 2, dc = 2.25 gcm-3 , final Rw - 0.070 for 903 reflections. The stacking of the nearly planar complex units along b leads to a polymeric structure where Cu is additionally coordinated by a Cl atom, and shows a loose interaction with an oxime N atom of an adjacent monomer. The EPR signal intensity shows Curie-Weiss behaviour in the temperature range 110 K-420 K.
Kernresonanzspektroskopische Untersuchungen an Organophosphorverbindungen - Thiophosphorylbromide RR′P(S)Br: R,R′=CH3, C2H5, i-C3H7, t-C4H9 / NMR Studies on Organophosphorous Compounds - Thiophosphorylbromides RR′P(S)Br (R, R′ = CH3, C2H5, i-C3H7, t-C4H9)
Authors: Peters Wilfried , Hagele Gerhard
Published: February 2015

1H NMR Spectra, 31P NMR Spectra NMR spectra of dialkylthiophosphoryl bromides RR′P(S)Br are analyzed. Methods are demonstrated for C2H5(i-C3H7)P(S)Br. A correlation between δ31ᴘ in the 31P NMR spectra and the number of β-methyl groups is discussed.
Simple Syntheses of 3-Substituted Indoles and their Application for High Yield 14C-Labelling
Authors: Schallenberg Jürgen , Meyer Eckart
Published: February 2015

Methods are described which allow the synthesis of several plant indole alkaloids and their metabolites at different scales. Compounds synthesized include gramine (1) (3-di-methylaminomethylindole) which is directly derived from indole, while its biosynthetic precursors 3-aminomethylindole (3) and 3-methylaminomethylindole (2) as well as indole-3-carboxylic acid (7) are synthesized via indole-3-aldehyde (6). Slight changes of the experimental conditions allow syntheses with high yields not only at the molar but also at the μmolar level. This is extremely useful when isotope labelled compounds of high specific radioactivity are required for studies of plant metabolism.
Bis(trimethylsiloxy)zinn(II): Ein Heterosiloxan als weicher Ligand / Bis(trimethylsiloxy)tin(II): A Heterosiloxane as Soft Ligand
Authors: Mont Wolf-Walther du , Grenz Mario
Published: February 2015

Contrary to earlier reports the reaction of sodium trimethylsilanolate with stannous chloride does not yield bis(trimethylsiloxy)tin(II) (1) but a polynuclear compound of the type Sn2O(OSiMe3)2 (2). 1 is obtained from the reaction of stannocene with trimethylsilanole. The compound is a dimer that gives rapid exchange reactions of terminal and bridging trimethylsiloxy groups in inert organic solvents.
C-13 NMR of Hecubine and Voaphylline, and a Study of Mass Spectral Fragmentation of Hecubine by Linked Scan Measurements
Authors: Rahman Atta-ur , Daulatabadi Nader , Smith D.
Published: February 2015

The C-13 NMR of hecubine and voaphylline are reported. The mass spectrum of hecubine has been studied by high resolution mass measurements, and the fragmentation patterns fol-lowed by a study of metastable ion transitions as determined by linked scan measurements.
Beiträge zur Chemie des Phosphors, 124 Tri-tert-butyl-diphosphastiba-cyclopropan, (t-BuP)2Sb(t-Bu)/Contributions to the Chemistry of Phosphorus, 124 Tri-tert-butyl-diphosphastiba-cyclopropane, (t-BuP)2Sb(t-Bu)
Authors: Baudler Marianne , Klautke Siegfried
Published: February 2015

The first three-membered P2Sb heterocycle, tri-tert-butyl-diphosphastiba-cyclopropane (tri-tert-butyl-diphosphastibirane) (1) was synthesized by [2+1] cyclocondensation of K(t-Bu)P-P(t-Bu)K with t-BuSbCl2 in n-pentane at -78 °C. Tetra-tert-butyl-1,2-diphospha- 3,4-distiba-cyclobutane (2), tetra-tert-butyl-triphosphastibacyclobutane (3) as well as (t-BuP)4 and five-membered cyclostibaphosphanes are also formed. Because of its hyperreactivity, 1 could not be isolated in a pure state. It forms two diastereomers, of which the isomer with trans-oriented tert-butyl groups at the phosphorus atoms is the more stable one. The 31P NMR parameters of the four-membered cyclostibaphosphanes 2 and 3 are reported.
Oxidationsreaktionen von Phosphanen mit Schwefeldioxid/Oxidation Reactions of Phosphanes with Sulfur Dioxide
Authors: Roesky Herbert W. , Djarrah Habib , Thomas Manfred , Krebs Berat , Henkel Gerald
Published: February 2015

Sulfur dioxide can be used as an oxidizer in the reaction of Zn(SO2)n(AsF6)2 and tetraphenyldiphosphane. The resulting product is the tetraphenyldiphosphane dioxide complex of composition Zn[O2P2(C6H5)4]3(AsF6)2 (1)-The same compound is formed by the direct reaction of the zinc salt with O2P2(C6H5)4.When Zn(S02)n(AsF6)2 is treated with P[O = P(OC2H5)2]3 in liquid SO2, Zn{P[O = P(OC2H5)2]3}2(AsF6)2 (2) is formed. The structure of 2 was investigated by means of an X-ray single crystal analysis. 2 crystallizes in space group P3̄1 c with a = b= 11.967(3) and c = 21.202(4) Å.

P[O = P(OC2H5)2]3 and (CO)4W(CH3CN)2 react to form (CO)4WP[O = P(OC2H5)2]3CH3CN.Only one acetonitrile molecule is replaced by the phosphane.
Darstellung und Kristallstrukturen einiger MSb5O13-Verbindungen (M = H3O, Na, K)/Preparation and Crystal Structure of Some MSb5O13 Compounds (M = H3O, Na, K)
Authors: Bodenstein Doris , Clegg William , Jäger Gerhard , Jones Peter G. , Rumpel Horst , Schwarzmann Einhard , Sheldrick George M.
Published: February 2015

Crystal Structure, Antimonate(V) The compounds MSbsOi3 (M = H3O, Na, K) have been prepared and characterised by chemical analysis and X-ray structure determination. They are isostructural, space group Cmem, with a = 657.7(2), 657.3(2), 658.4(2); b = 887.3(3), 888.7(2), 888.2(2); c = 1682.6(5), 1651.5(3), 1677.0(3) pm for M = H30, Na, K, respectively. The polymeric structures consist of SbOß octahedra linked via edges and vertices to form an Sb50i3 framework, in which the univalent cations occupy holes. Because these ions display severe disorder, X-ray methods alone would not be sufficient to establish the chemical constitutions.
Cs6Ga2Se6, ein ternäres Selenogallat(III) mit isolierten [Ga2Se6]6--Ionen/Cs6Ga2Se6, a Ternary Selenogallate(III) with Isolated [Ga2Se6]6- Ions
Authors: Deiseroth Hans-Jörg , Fu-Son Han
Published: February 2015

Cs6Ga2Se6 can be prepared from mixtures of Cs2Se and Ga2Se3. The transparent single crystals of the moisture sensitive compound (m.p. 685 °C) crystallize in the monoclinic system with a = 848.0(5), b = 1364.4(5), c = 1111.5(5) pm, β = 126.22(5)° (T = -150 °C, Z = 2, space group P21/c). The gallium atoms pairwisely occupy selected tetrahedral holes between layers formed by the cesium and selenium ions. This structural principle leads to the formation of double tetrahedral isolated [Ga2Se6] 6- ions.
Die Schwingungsfeinstruktur der elektronischen Absorptionsspektren von [OsO2(ox)2]2 -und [OsO2(mal)2]2-/ Vibrational Fine Structure on the Electronic Absorption Spectra of [OsO2(ox)2]2-and [OsO2(mal)2]2-
Authors: Preetz W. , Schulz H.
Published: February 2015

The complexes (TBA)2[OsO2(ox)2] and (TBA)2[OsO2(mal)2] have been prepared and characterized. The IR and Raman frequencies are assigned according to point group D2h. The electronic absorption spectra measured on thin films of the solid complex salts on silica discs at 10 K show well resolved vibrational fine structure. Two very weak bands (ε: 4-58) in the visible region are assigned to d-d transitions from the singlet ground state ag2 (dxy) to a triplet and singlet term of the equivalent π* orbitals b2g/b3g (dxz, dyz). The two more intense band systems (ε: 500-1500) in the UV region are attributed to CT transitions from b2u/b3u π orbitals of the oxo ligands to the lowest unoccupied orbitals b2g/b3g of the central ion. These electronic transitions couple with vs(Os = O) as indicated by the main progression of about 700 cm-1 . In comparison to the vibrational ground state this lowered frequency is caused by population of antibonding π levels. The loosening of the Os = O bonds in the excited state is demonstrated by high anharmonic constants (-2.5 to -10.5 cm-1) and the estimated bond lengthening of about 12 pm. Moreover the vibrational fine structure of the malonato complex shows many combination modes of vs(Os = O) with other symmetric fundamentals. Due to lower site symmetry in the solid state the CT transitions of the malonato compound are split into 2 components with a spacing of about 200 cm-1 .
2.2.5.5-Tetraorganyl-1.4-dioxa-2.5-disilacyclohexane/2,2,5,5-Tetraorganyl-1,4-dioxa-2,5-disilacyclohexanes
Authors: Tacke Reinhold , Lange Hartwig , Bentlage Anke , Sheldrick William S. , Ernst Ludger
Published: February 2015

The 2,2,5,5-tetraorganyl-1,4-dioxa-2,5-disilacyclohexanes 2a-2c were prepared by condensation of the corresponding (hydroxymethyl)diorganylsilanes 1 a-1 c. The constitution of the heterocycles was confirmed by elemental analyses, cryoscopic measurements, mass spectrometry, and NMR-spectroscopic (1H, 13C) investigations. The molecular structure of 2 b was determined by X-ray diffraction analysis.
Die Reaktion zwischen Schwefel bzw. Kohlenstoflfdisulfid und Natriumboranat in Aminen. Zwei neue Darstellungsmethoden für Alkylaminborane, R3-nHnN-BH3/The Reaction between Sulfur or Carbon Disulfide Respectively, and Sodium Borohydride in Amines Two New Methods for the Preparation of Alkylamine Boranes, R3-nHnN-BH3
Authors: Binder Herbert , Diamantikos Wassilios
Published: February 2015

Sodium borohydride reacts with sulfur in ammonia, primary, secondary or tertiary amines with hydrogen evolution to give the corresponding amine boranes, R3-nHnN-BH3. The reaction of sodium borohydride with carbon disulfide in the presence of a tertiary amine yields compounds R3N-BH3. The formulation of these reactions has been established by 11B and 1H NMR.
Kristallstruktur von Pyrrolidinium-bis(diisopropylphosphinoyl)phosphid, einem System mit zweifach koordiniertem Phosphor /Crystal Structure of Pyrrolidinium-bis(diisopropylphosphinoyl)phosphide, a System with Bicoordinated Phosphorus
Authors: Weber Dieter , Peters Karl , Schnering Hans Georg von , Fluck Ekkehard
Published: February 2015

Pyrrolidinium-bis(diisopropylphosphinoyl)phosphide crystallizes triclinically in the space group P1̄ with a = 1019.6(8), b = 1271.5(4), c = 999.5(7) pm, a = 100.90(5)°, β = 91.24(5)°, γ = 99.10(5)° and Z = 2 formula units. The mean P-P bond length is 212.2 pm and hence shorter than in derivates in which the electron pairs of the bicoordinated phosphorus atom are bonded to one or two M(CO)5-groups. Additional pπ-dπ bonding explains the shortening of the P-P bond.
Untersuchungen zur reduktiven Eliminierung des Biphenyl-Systems aus substituierten cis-Bis(phenyl)bis(triphenylphosphan)platin(II)-Verbindungen/On the Reductive Elimination of the Biphenyl System from Substituted cis-Bis(phenyl)bis(triphenylphosphane)platinum(II) Compounds
Authors: Bayer Ulrich , Brune Hans Albert
Published: February 2015

The Compounds cis-[Pt(PPh3)2(4-X-C6H4)2] [X = F, Cl, CF3, OCH3, N(CH3)2] and cis-[Pt(PPh3)2(4-X-C6H4)(Y-C6H4)] [X = F/Y = 3 Cl, 4-C1, 3-CH3O, 4-CH3O; X = CF3/Y = 3-F, 4-F] have been synthesized and studied thermally with respect to the reductive elimination of disubstituted biphenyls. Activation parameters ⊿H≠ and ⊿ S≠ are reported and discussed.
Synthese und pharmakologische Eigenschaften von silylierten Dopaminen und 4.4-Diphenylpiperidinen/Synthesis and Pharmacological Properties of Silylated Dopamines and 4,4-Diphenylpiperidines
Authors: Gerlach Manfred , Jutzi Peter , Stasch Johannes-Peter , Przuntek Horst
Published: February 2015

Syntheses for the bis-O-trimethylsilylated (2), the tris-O,O,N-trimethylsilylated (3) and the tetrakis-O,O,N,N-trimethylsilylated dopamine (4) are described. The preparation of some N-trialkylsilylated 4,4-diphenylpiperidines 6-8 and of the N-triphenylsilylated piperidine 9 is also reported. The silylation of these neuropharmaca enhances their lipophilic character. Preliminary pharmacological investigations show the desired central effect of these compounds. The silylated dopamines 3 and 4 influence positively the rigid akinetic syndrom, which was induced by reserpine. The silylated 4,4-diphenylpiperidines 6-9 show the same effect on the content of neurotransmitters in the rat brain as the Antiparkinson drug 1-tert-butyl-4,4-diphenylpiperidine (budipine).
Two New Reagents for the Fluorescence Derivatization of NH and OH Containing Compounds
Authors: Wintersteiger Reinhold , Wolfbeis Otto S.
Published: February 2015

The synthesis of three new reagents, namely the bromomethyl derivatives of a pyrano-[3,2-c]benzopyran (2b) and of 11H-pyrido[1,2-b]quinazolin-11-one (3b, d) is described. Introduction of the reactive bromomethyl group was accomplished in one case (2 b) by a ring closure reaction using ethyl y-chloroacetoacetate, and in the other cases (3 b, d) by bromination of a methyl group using N-bromosuccinimide. 2 b is suitable for the derivatization of barbiturates, whilst 3d reacts with oxygen nucleophiles like alcohols, phenols or carboxylates.
Fluoreszenz und Struktur von Flavonen, II Der Einfluß von Hydroxygruppen in 6-, 8-und 2′-Stellung*/Fluorescence and Structure of Flavones, II The Influence of Hydroxy Groups at Positions 6, 8 and 2′*
Authors: Geiger Hans , Homberg Harald
Published: February 2015

The fluorescence spectra of various 2′-, 6-and 8-hydroxy-, methoxy-, and glucosyloxy-flavones adsorbed on cellulose alone and with added shift reagents are reported. The correlation between fluorescence and structure of these compounds is discussed.
Angriff eines lithiierten Aminofluorsilans auf die C-O-Bindung des Cr(CO)6; Bildung von Isonitrilkomplexen/Attack by a Lithiated Aminofluorosilane on the C - O Bond of Cr(CO)6; Formation of Isonitrile Complexes
Authors: Clegg William , Klingebiel Uwe , Sheldrick George M.
Published: February 2015

The photochemical reaction of a lithiated aminofluorosilane with Cr(CO)6 leads to substitution of one or two carbonyl oxygen atoms and formation of isonitrile complexes. The crystal structure of the disubstituted product, cis-di(tert-butylisonitrile) tetracarbonylchromium, has been determined.
Komplexe des Cu(I), Ag(I) und Rh(III) mit Nitronylnitroxylradikalliganden/Complexes of Cu(I), Ag(I) and Rh(III) with Nitronylnitroxylradicals as Ligands
Authors: Dorfer Astrid , Schwarzhans Karl E.
Published: February 2015

The stable free radical 4,4,5,5-tetramethyl-imidazoline-1-oxyl-2-p-pyridyl-3-oxide (L1) has been prepared and used as a ligand in copper (I), silver(I) and rhodium(III) complexes, the meta isomer (L2) as a ligand in a rhodium(III) complex, too. The magnetic moments and the EPR spectra of the free radicals and the complexes have been investigated. A solvent and temperature dependent intramolecular interaction between the radicalic ligands was found in the silver(I) complex, but in none of the complexes any intramolecular interaction between the metal ions and the unpaired electrons of the ligands could be observed.
Alternativ-Liganden, XIV [1]. Neue Chelatliganden des Typs (2-Me2E′C6H4)Si(EMe2)Me2 (E, E′ = N, P, As; Me = CH3) / Alternative Ligands, XIV [1]. Novel Chelating Ligands of the Type (2-Me2E′C6H4)Si(EMe2)Me2 (E, E′ = N, P, As; Me = CH3)
Authors: Aslanidis Paraskevas , Grobe Joseph
Published: February 2015

Chelating ligands of the type (2-Me2NC6H4)Si(EMe2)Me2 (E = N, P, As) are prepared by ortho-lithiation of N,N-dimethylaniline followed by reaction with ClSi(NMe2)Me2 to yield (2-Me2NC6H4)Si(NMe2)Me2. Cleavage of the SiN-bond with MePCl2 affords (2-Me2NC6H4)Si(Cl)Me2, which on substitution with LiEMe2 (E = P, As) gives the corresponding ligands. Synthesis of (2-Me2E'C6H4)Si(EMe2)Me2 with E' = P or As is accomplished by producing 2-ClC6H4MgBr followed by reaction with either Me2E'Cl or ClSi(NMe2)Me2 to yield (2-ClC6H4)E'Me2 and (2-ClC6H4)Si(NMe2)Me2, respectively. The second donor group is introduced by Cl/Li exchange and reaction of the resulting lithium compounds with either ClSi(NMe2)Me2 or Me2E'Cl. (2-Me2PC6H4)Si(NMe2)Me2 and (2-Me2AsC6H4)Si(NMe2)Me2 then are used to prepare the additional four ligands with E, E' = P, As via (2-Me2E'C6H4)Si(Cl)Me2 by substitution with LiEMe2.
Alternativ-Liganden, XV [1]. Neue Liganden des Typs (4-XC6H4)SiMe(EMe2)CH2CH2E′Me2 (E, E′ = N, P, As; X = Cl, F; Me = CH3) / Alternative Ligands, XV [1]. Novel Ligands of the Type (4-XC6H4)SiMe(EMe2)CH2CH2E′Me2 (E, E′ = N, P, As; X = Cl, F; Me = CH3)
Authors: Aslanidis Paraskevas , Grobe Joseph
Published: February 2015

Starting from Cl2Si(Me)CH = CH2 (1) the title compounds are obtained by two different routes:

a) Ligands with E = N and E' = N, P, As are prepared by aminolysis of 1 yielding Cl(Me2N)Si(Me)CH = CH2 (2) followed by SiCl-substitution with (4-ClC6H4)MgCl (3). Photochemical or base catalyzed addition of HE'Me2 (E' = N, P, As) to the vinyl group of (4-ClC6H4)SiMe(NMe2)CH = CH2 (4) produces the corresponding ligands 5 to 7 (Abb. 2). Cleavage of the SiN bond in 7 leads to (4-ClC6H4)SiMe(Cl)CH2CH2NMe2 (8) which on substitution with LiEMe2 (E = P, As) gives the ligands 9 and 10.

b) Ligands with E, E' = P, As are obtained by first introducing the aryl substituent to yield (4-ClC6H4)SiMe(Cl)CH = CH2 (11) which by photochemical addition of HE'Me2 (E' = P, As) gives the semi-ligands 12 and 13. Replacement of SiCl by SiEMe2 (E = P, As) with LiEMe2 affords compounds 14 to 17 (Abb. 3). - Some representative ligands with p-fluorophenyl groups (19, 20, 24, 25) are prepared by similar procedures (Abb. 4). New compounds are characterized by spectroscopic methods (IR, NMR, MS).
Darstellung and Kristallstruktur von [(C6H5)4As]2M(NO3)5 (M = Ho, Er, Tm, Yb) / Preparation and Crystal Structure of [(C6H5)4As]2M(NO3)5 (M = Ho, Er, Tm, Yb)
Authors: Urland W. , Warkentin E.
Published: February 2015

The compounds [(C6H5)4As]2M(NO3)5 (M = Ho, Er, Tm, Yb) were prepared and investigated by X-ray diffraction. It has been found that they are isotypic with [(C6H5)4As]2Eu(NO3)5. The structure was refined by single crystal data for [(C6H5)4As]2Er(NO3)5.
Über die Staudinger-Reaktion mit Tantaltetrachloridazid. Die Kristallstruktur von Tantal(V)-(triphenylphosphinimino)tetrachlorid, Ta[NP(C6H5)3]Cl4 / On the Staudinger Reaction with Tantalum Tetrachloride Azide. The Crystal Structure of Tantalum(V)(triphenyl-phosphinimino)tetrachloride, Ta[NP(C6H5)3]Cl4
Authors: Bezler Hans , Strähle Joachim
Published: February 2015

[TaCl4N3]2 reacts easily with PPh3 yielding TaCl4(NPPh3 ) , TaCl4(NPPh3)(NHPPh3) and TaCl5 . The latter are supposed to be products of the reaction of primarily formed TaCl4(NPPh3)2-TaCl4
+ with the solvent ClCH2-CH2Cl. TaCl4(NPPh3) crystallizes in the monoclinic system with the space group P21/c. The crystal structure shows centrosymmetric dimers, in which the Ta atoms are linked together by asymmetric Cl bridges. The phosphinimino ligand is coordinated trans to the Cl bridge and causes a strong trans effect. A linear P = N = Ta group with double bonds of P = N = 159.3 and Ta = N = 180,1 pm is observed.
Bor- und Arsen-methoxotetrafluorotellurate(VI) / Boron and Arsenic Methoxotetrafluorotellurates(VI)
Authors: Tötsch Walter , Aichinger Heinrich , Sladky Fritz
Published: February 2015

The interaction of cis-and trans-HOTeF4OCH3 with BCl3 yields B(cis-and trans-OTeF4OCH3)3. The ability of these compounds to transfer the CH3OTeF4O entities has been demonstrated in reactions with AsF3, with the formation of As (cis-and trans-OTeF4OCH3)3 respectively. All compounds have been characterized by NMR spectroscopy (125Te, 19F, 11B, 1H).
Molekülstrukturen, Schwingungsspektren und Konformation der Thiooxalsäurederivate CH3S-CO-CONH2, CH3S-CS-CONH2, C2H5O-CO-CSNH2 und K[OSC-CONH2] / Molecular Structure, Vibrational Spectra and Conformation of the Thiooxalic Acid Derivatives CH3S-CO-CONH2, CH3S-CS-CONH2, C2H5O-CO-CSNH2 and K[OSC-CONH2]
Authors: Mattes Rainer , Waldmann Franz
Published: February 2015

The crystal structures of CH3S-CO-CONH2 (1), CH3S-CS-CONH2 (2), C2H5O-CO-CSNH2 (3) and K[OSC-CONH2] (4) have been determined by single crystal X-ray diffraction. The molecules 1, 2 and 3 are nearly planar and form centrosymmetric dimers by N H···O or N-H···S hydrogen bonds with the amidic oxygen or sulfur atom as acceptor atoms. The anion of 4 is not quite planar. The torsional angle around the C-C bond is 18.4°. The conformations of the title compounds are E, Z' (1 and 2), Z, Z' (3) and Z (4). According to the vibrational spectra, which are discussed briefly, 1 and 3 retain their conformation also in solution.
Deprotonated Complexes of Bis(o-aminobenzenesulfonyl)ethylenediamine with Mn(II), Co(II), Ni(II) and Cu(II)
Authors: Perlepes S. P. , Zafiropoulos Th. F. , Galinos A. G. , Tsangaris J. M.
Published: February 2015

The new complexes K2[ML2] (M = ═Mn, Cu), K2[ML2(H2O)2] (M = Co, Ni), K2[Cu2L2(OH)2] and K2[Cu2L2(OH)2(H2O)4], where LH2 = Bis(o-aminobenzenesulfonyl)ethylenediamine, have been prepared. Properties, X-ray powder patterns, molar conductance measurements, magnetic moments and spectral (IR, diffuse reflectance, visible in solution) data are discussed in terms of possible structural types and the nature of the bonding.

Distorted octahedral geometries are proposed for the Mn(II), Co(II), Ni(II) and dimeric Cu(II) chelates in the solid state, while K2[CuL2] appears to have a distorted tetrahedral structure. The Mn(II) complex exhibits evidence of a polymeric configuration. The L 2- anion acts as a bidentate N2 or tetradentate N4 ligand.
Metallomethane, VI [1]. Kristallstruktur von Tetrakis(chloroquecksilber)methan-Dimethylsulfoxid C(HgCl)4 · (CH3)2SO / Metallomethanes, VI [1]. Crystal Structure of Tetrakis(chloromercuri)methane-Dimethylsulfoxide C(HgCl)4 · (CH3)2SO
Authors: Breitinger Dietrich K. , Petrikowski Günter , Liehr Günter , Sendelbeck Raymond
Published: February 2015

The tetrakis (halomercuri) methane dimethylsulfoxide solvates C(HgX)4 · DMSO (X = Cl and Br) have been prepared. - The crystal structure of the chloro compound C(HgCl)4 · DMSO has been determined (R = 0.0611 and Rw = 0.0562). The compound crystallizes in space-group P21/n with a = 1854(1) pm, b = 727.3(5) pm, c = 1049.1(6) pm, β = 94.82(3)°, Z = 4; dc = 4.873 g·cm-3, d0 = 4.51 g-cm-3. - The C(HgCl)4 molecules have C-Hg bond lengths in the range 201.4(26) to 209.9(27) pm (average 207.0 pm), and Hg-Cl bonds between 231.4(9) and 234.2(9) pm (average 233.2 pm). The bond angles Hg-C-Hg vary from 107.3(3) to 111.7(4)° (average 109.5°), and the angles C-Hg-Cl are found within the limits 172.2(24) and 178.3(25)° (mean 174.3°). DMSO molecules (S-O bond 148.6(23)pm) are coordinated via oxygen to two Hg atoms of one C(HgCl)4 molecule and to one Hg atom of a neighbouring C(HgCl)4 molecule forming two bifurcated bridges in a dimer [C(HgCl)4 · DMSO]2; two strong Cl→···Hg and two weak S→···Hg interactions also contribute to this pair formation. The dimeric units are arranged to layers in the planes (100) and (200), such that each C(HgCl)4 molecule has six C(HgCl)4 and two DMSO molecules as neighbours; with two C(HgCl)4 molecules from each adjacent layer, each C(HgCl)4 molecule achieves a total coordination number of ten. Depending on the van der Waals radius assumed for mercury a packing coefficient 0.640 ≤ k ≤ 0.691 is obtained. - Cryoscopy and vibrational spectrometry suggest monomeric, unperturbed tetrahedral C(HgX)4 molecules in DMSO solutions.
Reaktionen von S-Methylthiireniumsalzen mit nucleophilen Übergangsmetall-Komplexen [1] / Reactions of S-Methylthiirenium Salts with Nucleophilic Transition Metal Complexes [1]
Authors: Götzfried Franz , Beck Wolfgang
Published: February 2015

Abstract 1

-Methyl-2,3-di-t-butyl-thiirenium-tetrafluoroborate (1) reacts with K + [π-C5H5(CO)3Mo] and (PPh3)4Pt to give [(π-C5H5)(CO)2MoSCH3]2 and [(Ph3P)3PtSCH3]+BF4
-, respectively. With 1 and (Ph3P)4Pd the phosphonium salt [Ph3PSCH3]+BF4-has been isolated.
Derivate des 1.3-BenzdioxoIs, 48 [1]. Darstellung und Reaktionen von substituierten 1.3-Benzdioxol-4.7-cliinonen / Derivatives of 1,3-Benzdioxoles, 48 [1]. Preparation and Reactions of 1,3-Benzdioxole-4,7-quinones
Authors: Dallacker Franz , Holtmann Bodo , Coerver Wim
Published: February 2015

We describe the preparation of a substituted 1,3-benzdioxole-4,7-quinonecomplex (2) by reaction of 4-hydroxy-1,3-benzdioxole (1) with potassiumnitrosodisulfonate.

The quinones 4a-d can be obtained by treatment of the 4-hydroxy-7-methoxy-1,3-benzdioxoles 3 a-d with ammoniumcerium(IV)nitrate. Reaction of 2 with several cyclophiles gives the addition compounds resp. the dehydrogenation-products 6b-d in partly high yields.
Ylide von Heterocyclen, V [1]. I-, N-und S-Ylide des 2-Pyrons und 2-Pyridons / Ylides of Heterocycles, V [1]. I-, N-and S-Ylides of 2-Pvrones and 2-Pyridones
Authors: Kappe Thomas , Korbuly Gertraud , Pongratz Erik
Published: February 2015

The reaction of the pyrone 1 a or the pyridones 1 b, c with iodosobenzene leads to the iodonium-ylides 2 which undergo thermal rearrangement to the 4-phenyloxy-3-iodo compounds 3. Reductive deiodination of 3 gives the 4-phenyloxy compounds 4. By acid catalyzed treatment with nucleophiles (such as pyridine, nicotinamide, isoquinoline and thiophane) the iodonium-ylides 2 can be converted into the corresponding N- and S-ylides 5. Reaction of 2 with concentrated HCl or HBr gives the 3-halogeno substituted compounds 6.
NOTIZEN. Darstellung und Struktur von Ba6Sn2P6 / Preparation and Crystal Structure of Ba6Sn2P6
Authors: Eisenmann Brigitte , Jordan Hanna , Schäfer Herbert
Published: February 2015

The new compound Ba6Sn2P6 crystallizes in the monoclinic system, space group P21/c with lattice constants

a = 883.7 ± 0.5 pm

b = 1268.8 ± 0.8 pm

c= 862.3 ± 0.5 pm

β = 114.42 ± 0.10°.

The compound is isotypic to K6Sn2Te6 and contains the Sn2P6
12- -anions which are isosteric with the Sn2Te6
6- -units.
Über neue Cyano-nitrosylmanganate und Isonitril-nitrosyl-Komplexe des Mangans/On New Cyano Nitrosyl Manganates and Isonitrile Nitrosyl Complexes of Manganese
Authors: Moll Matthias , Behrens Helmut , Trümmer Karl-Heinz , Merbach Peter
Published: February 2015

The anionic cyano nitrosyl manganates [Mn(NO)(CO)3CN] - and [Mn(NO)3CN]- are formed by the reactions of Mn(NO)(CO)4 and Mn(NO)3CO with NaN(SiMe3)2. The alkylation of these anions with [R3O]BF4 (R = Me, Et) leads to the corresponding isonitrile complexes Mn(NO)(CO)3CNR and Mn(NO)3CNR. IR, mass and 13C NMR spectra indicate trigonal-bipyramidal coordination for nitrosyl tricarbonyl derivatives, with three CO ligands in facial positions and NO in the equatorial plane. Based on the temperature dependent 13C NMR spectra of Mn(NO)(CO)3CNR and Mn(NO)(CO)4 the fluctional behaviour of these compounds could be demonstrated with ⊿G+ values of 48 kJ/mol or less for the CO exchange.
Beiträge zur Chemie des Phosphors, 125/Synthese und Struktur der Triorganyl-nonaphosphane(3) P9(i-Pr)3 und P9 (t-Bu)3
Authors: Baudler Marianne , Aktalay Yusuf , Kazmierczak Karin , Hahn Josef
Published: February 2015

The triorganyl-nonaphosphanes(3) P9(i-Pr)3 (1) and P9(t-Bu)3 (2) have been obtained by reacting (i-PrP)4 with PCl3 and by dehalogenating a mixture of t-BuPCl2 and PCl3 with magnesium, respectively. In the case of P9Et3 (3) and P9Me3 (4) the latter reaction may be modified by using the organyl-cyclophosphanes (PR)n instead of RPCl2. P7R3 as well as other polycyclic organylphosphanes are formed as by-products. 1 could be isolated in pure form and 2 has been concentrated in the product mixture. According to their 31P{1H}-NMR spectra 1-4 possess a P9 skeleton analogous to that of the hydrocarbon deltacyclane. 1 and 2 are formed as mixtures of two configurational isomers, which differ in the spatial arrangements of the substituent on P5. The results clearly indicate, that the corresponding phosphorus hydride P9H3 has the same structure and is a tetracyclo[4.3.0.02,4.03,7]nonaphosphane.
Darstellung von trans-[PtCl4Br2] 2 -und [PtCl5Br] 2- durch oxidative Addition an [PtCl4]2-/Preparation of trans-[PtCl4Br2] 2--and [PtCl5Br] 2 -by Oxidative Addition to [PtCl4]2-
Authors: Preetz W. , Rimkus G.
Published: February 2015

The oxidative addition of Br2 to [PtCl4]2-in HBr yields almost pure trans-[PtCl4Br2]2-, in HCl nearly pure [PtCl5Br]2-, and in CH2Cl2 by a quantitative and stereospecific reaction completely pure trans-[PtCl4Br2]2-. This is confirmed by ion exchange chromatography on diethylaminoethyl cellulose and by analysis of the vibrational spectra in comparison with the IR and Raman spectra of the well-known species of the series [PtClnBr6-n]2- , n = 0-6. The literature concerning trans-[PtCl4Br2]2- and other mixed ligand complexes is critically discussed.
Reactions of Fluorinated Nitriles with Sulphur(II) Chlorides; Crystal Structure of 2,4,6-Tris(difluorosulphoximido)-1,3,5-triazene at 170 K
Authors: Höfs Hans-Ulrich , Mews Rüdiger , Noltemeyer Mathias , Sheldrick George M. , Schmidt Martin , Henkel Gerald , Krebs Bernt
Published: February 2015

The addition of CF3SCl (2) to the fluorinated nitriles RfCN[Rf = CF3 (3), NSF2 (4), NSOF2 (5)] leads to N-perfluoromethanesulphenyl-formylimidoylchlorides CF3S-N = C(Cl)Rƒ (6, 11, 12). From the reactions of SCl2 (1) with (3) and (5), which yielded the N-sulphenyl-chlorides ClS-N = C(Cl)-Rƒ(7, 13), it proved possible also to isolate the oxidation product [CF3CCl2NSCl2 (8)] and an oligomer of the nitrile [(NCNSOF2)3 (14)]. Dechlorination of 7 with Hg gives the corresponding di-and tri-sulphides (CF3C(Cl) = N-)2Sx; (9, 10, x =2, 3). Crystals of (14) are triclinic with a = 1133.6(5), b = 1332.6(5), c = 1715.1(8) pm, α = 109.31(3), β = 105.30(3), γ = 97.84(3)° at 170 K, Z = 8, space group P1̄. The structure was refined to R = 0.028 for 8290 diffractometer data with F > 4σ (F). The four crystallographically independent molecules adopt similar unsymmetrical conformations.
Eisen(III)phthaloeyanine: Darstellung und spektroskopische Charakterisierung von [Fe(OR)2Pc(—2)]- (R = H, CH3, C2H5, (CH3)2CH, (CH3)3C), (FePc(—2))2O und FeXPc(—2) (X = F, Cl, Br, I)/ Iron(III)phthalocyanines: Preparation and Spectroscopic Characterisation of [Fe(OR)2Pc(—2)]- (R = H, CH3, C2H5, (CH3)2CH, (CH3)3
C), FePc(—2))2O and FeXPc(—2) (X = F, Cl, Br, I)
Authors: Kalz W. , Homborg H.
Published: February 2015

The preparation of bis-hydroxophthalocyaninatoferrate(III) and of some of the bis-alkoxo-analogues is described. In the presence of a small excess of OR -(R = H, CH3, C2H5, (CH3)2CH, (CH3)3C) these complexes are stable in most common non-polar solvents and can be isolated as analytically pure bis-triphenylphosphiniminium-(PNP)-salts. Solutions of these complexes react immediately with water and acids. Thus hydrolysis is an easy way to prepare μ-oxo-bis-phthalocyaninatoiron(III). The reaction with mineral acids HX (X = F, Cl, Br, I) precipitates the pure pentacoordinated halogenophthalocyaninatoiron-(III). The electronic absorption spectra have been measured. Besides the typical inner-ligand π-π*-transitions additional bands are observed at ~11,5kK (CT1) and ~20kK (CT 2). These bands are of medium intensity only for FeXPc(-2) (X = Cl, Br, I) especially in the solid state spectra and are probably associated with ligand-to-metal-charge-transfer(CT)-transitions mainly of the Pc → Fe-type but partially mixed with X→Fe. CT 1 and CT2 are assigned to (a1)π → (e,a1)d respectively. This is confirmed by the resonance Raman spectra. On excitation within the range of the CT 2 electronic transition some in-plane stretching-(1595 and 1550 cm -1) and out-of-plane deformation vibrations (350 and 290 cm -1) of the macrocycle as well as the Fe-X-stretching vibrations are resonance Raman enhanced. Combination bands of Fe-X-with Pc-vibrations give strong evidence for coordination of the halide to an axial position of the iron centre. As expected for C4V point symmetry the Fe-X vibrations are IR active, too (ν(Fe-X) for X = F: 475; Cl: 303; Br: 221; I: 193 cm -1). The Fe-O stretching vibration (a1g) is only observed in the resonance Raman spectrum of PNP[Fe(OH)2Pc(-2)] at 495 cm -1 . As a consequence of the strong antiferromagnetic coupling the IR and resonance Raman spectra of (FePc(-2))2O resemble those of closed shell ions. The IR absorption at 822 cm-1 is assigned to the anti-symmetric (a2u) (Fe-O-Fe) deformation mode.
Azaborolinyl-Komplexe, IX Die Kristall- und Molekülstrukturen von zwei Isomeren des Bis(1-tert-butyl-2-methyl-η-1.2-azaborolinyl)cobalts/Azaborolinyl Complexes, IX The Crystal and Molecular Structures of Two Isomers of Bis(1-tert-butyl-2-methyl-η-1,2-azaborolinyl)cobalt
Authors: Schmid Günter , Boese Roland
Published: February 2015

The crystal and molecular structures of two isomers of bis(1-tert-butyl-2-methyl-η-1,2-azaborolinyl)cobalt have been determined by single-crystal X-ray diffraction methods. Isomer 1 shows a clockwise, isomer 2 an anti-clockwise conformation of the azaborolinyl rings. In both compounds the azaborolinyl rings have staggered orientations with opposite positions of the tert-butyl groups. The rings in 1 and 2 are slipped so that the three ring carbon atoms are closer to the cobalt atom than the BN groups. The staggered orientation of the ligands in 2 is probably due to a packing effect, as in similar sandwich complexes the anti-clockwise conformers show eclipsed orientation.
Synthese von 3-Methylenmonosubstituierten-2-oxo-tetxahydrofuranen aus 3-Phosphonolactonen/Synthesis of 3-Methylenmonosubstituted-2-oxo-tetrahydrofurans from 3-Phosphonolactones
Authors: Falsone Giaocchino , Peters Wilfried
Published: February 2015

The synthesis of 3-methylenmonosubstituted-2-oxo-tetrahydrofurans 3 a-f from 3-phosphonolactones 1 a-b and the aldehyds 2a-d is described. 1H NMR spectra of the 3-methylenmonosubstituted-2-oxo-tetrahydrofurans are discussed.
Stereospecific Synthesis of 4,8-Dimethylspiro(4,5)-deca-7-ene-1,6-dione A Synthetic Route to the Acoranes
Authors: Michelotti E. L. , Sanchez E. L.
Published: February 2015

A stereospecific synthesis of 4,8-dimethylspiro(4,5)-deca-7-ene-1,6-dione from 4,7-dimethylcoumarine in high yield is reported. The configuration of this product is established according to its 1H NMR and 13C NMR data.
The Photoelectron Spectra of Cyclic Peroxylactones
Authors: Böhm Michael C. , Adam Waldemar , Narita Nozomu
Published: February 2015

The He(I) photoelectron spectra of the five-membered and six-membered peroxylactones 1 and 2 have been recorded and are analyzed on the basis of MINDO/3 calculations. A strong destabilization of the peroxo η-combination due to the adjacent carbonyl group is found. In 2 the usual peroxide sequence (π_ on top of n_) is reversed.
Cycloadditionen von Ketenen mit Fulvenen/Cycloadditions of Ketenes with Fulvenes
Authors: Friedrichsena Willy , Debaerdemaeker Tony , Böttcher Andreas , Hahnemann Sabine , Schmidt Regine
Published: February 2015

Fulvenes (1) add ketenes (2) in a [ π 2 + π 2] manner to give bicyclo[3.2.0]heptenes (3). Ring cleavage with sodium methoxide yields dihydrofulvenes (4) which can be deliydrogenated to give fulvenes (5), whereas the acid catalyzed ring opening reaction of 3 leads to fulvenes (6). The structure of 3h has been clarified by X-ray crystallography.
Weitere aus dem Kulturmedium von Pseudomonas putida isolierte Pyridinderivate -Genuine Metaboliten oder Artefakte ?/Further Pyridine Derivatives Isolated from the Culture Medium of Pseudomonas putida - Genuine Metabolites or Artefacts ?
Authors: Budzikiewicz H. , Hildebrand U. , Ockels W. , Reiche M. , Taraz K.
Published: February 2015

From the culture medium of Pseudomonas putida after treatment with CH2N2 besides the expected Pyridine-2,6-di(monothiocarboxylic acid)-di-S-methyl ester a series of pyridine derivatives could be isolated which could be shown to be artefacts formed from pyridine-2,6-di(monothiocarboxylic acid).
Notizen: Übergangsmetall-Schwefel-Stickstoff- Komplexe, II Ni(S2N2H)2 als S2N2-Synthon: Ein neuer Weg zu cyclischen Schwefel-Stickstoff-Verbindungen/Transition Metal Sulfur-Nitrogen-Complexes, II Ni(S2N2H)2 as S2N2-Synthon: A New Way to Cyclic Sulfur Nitrogen Compounds
Authors: Heitmann Axel , Edelmann Frank
Published: February 2015

Facile syntheses of S3N2O, S2N2CO and S4N2 from Ni(S2N2H)2 are described.
Notizen: Die Kristallstruktur des Bleisulfits/Crystal Structure of Lead Sulfite
Authors: Lutz Heinz Dieter , Buchmeier Willi , Engelen Bernward
Published: February 2015

The crystal structure of orthorhombic PbSO3 (Pnma, Z = 4, a = 790.3(1), b = 548.8(1), c = 680.2(1) pm) has been determined using single crystal X-ray diffraction data (final R for 663 reflections with I ≥ 2σ(I) = 0.052). The parameters of the atoms in the asymmetric unit are: Pb(4c) 0.68444(8), 0.25, 0.36072(8); S(4c) 0.5362(5), 0.25, 0.8470(5); O1(4c) 0.686(2), 0.25, 0.981(2); O2(8d) 0.563(1), 0.471(2), 0.712(1). The sulfite ion has S-O distances of 149.4(7) and 153.7(5) (twice) pm. The Pb-O distances of the edge-connected Pb-O7 polyhedra (distorted mono-capped trigonal prism) range from 253.4(5) to 284.8(5) pm. The structure is closely related to that of PbSO4.
Notizen: Schwingungseigenschaften des Nitrat-Ions im Ba10(ReO5)6(NO3)2-Apatit/Vibrational Properties of the Nitrate Ion in the Ba10(ReO5)6(NO3)2-Apatite
Authors: Baran E. J. , Aneas M. , Besse J.-P.
Published: February 2015

The infrared and Raman spectra of the crystalline Ba10(ReO5)6(NO3)2 apatite are reported and the vibrational properties of the NO3-ion present in this lattice are discussed in detail.
Notizen: Imidazolkatalysierte Umwandlung von 2-Arylmethylperhydro-1.5.2-dioxazin- 3.6-dionen in 4-0xazolidinone/Imidazole Catalyzed Transformation of 2-Arylmethylperhydro-1,5,2-dioxazine- 3,6-diones into 4-Oxazolidinones
Authors: Geffken Detlef
Published: February 2015

In boiling toluene 2-arylmethylperhydro- 1,5,2-dioxazones (1) undergo imidazole catalyzed ring transformation into 4-oxazolidinones (5) or decompose into glyoxylamides 4.
Untersuchungen an Polypseudohalogeniden, II. Darstellung und Kristallstruktur des Rubidiumdicyanotriiodids, Rb[I(ICN)2]/ Studies on the Polypseudohalides, II. Preparation and Crystal Structure of Rb[I(ICN)2]
Authors: Tebbe Karl-Friedrich , Fröhlich Roland
Published: February 2015

The new compound Rb[I(ICN)2] can be prepared in aqueous solution by simple addition of two mole equivalents of ICN to one formula unit Rbl. The solid is isotypic with Cs[I(ICN)2] and crystallizes in the orthorhombic space group Pmmn with a = 16.246 Å, b = 6.795 Å, c = 4.397 Å and Z = 2. The crystal structure has been solved from diffractometer data and refined to R = 0.035 for 313 observed reflections.

The structure may be interpreted as a layer-like package of Rb+ cations and pentahalideanalogous anions [I(ICN2]-. The anionic groups are angular with symmetry mm 2 and φ ( I-I-- I ) = 128.69°, φ(I--I-C) = 175.5°, φ=(I-C-N) = 177°, d(I--I) = 3.271 Å, d(I-C) = 2.11 A, d(C-N) = 1.13 A. The cation is surrounded by a distorted cube of iodine atoms with a minimum distance d(Rb-I) = 3.775 Å.

Some additional results on the reactions of alkali halides and halogenocyans in different solvents are mentioned and compared with those described elsewhere.
Übergangsmetall-Carben-Komplexe, CXXX. Nucleophile Spaltung der Kohlenstoff-Fluor-Bindung in einem Fluorcarben-Komplex des Mangans/ Transition Metal Carbene Complexes, CXXX. Nucleophilic Cleavage of the Carbon-Fluorine Bond in a Fluorocarbene Complex of Manganese
Authors: Fischer Ernst Otto , Chen Jiabi
Published: February 2015

The reaction of C5H5(CO)2Mn[C(C6H5)F] with n-C4H9Li results in cleavage of the C(carbene)-F bond and formation of C5H5(CO)2Mn[C(C6H5)n-C4H9]. In a similar way fluoride can be abstracted by ethanol to yield C5H5(CO)2Mn[C(C6H5)OC2H5].
Mikrobiologische Umwandlung von Silicium-Yerbindungen: Enantioselektive Reduktion von Acetessigsäure-(trimethylsilylalkyl)estern und deren Carba-Analoga/ Microbiological Transformation of Silicon Compounds: Enantioselective Reduction of Trimethylsilylalkyl Acetoacetates and their Carba-Analogues
Authors: Tacke Reinhold , Linoh Haryanto , Stumpf Burghard , Abraham Wolf-Rainer , Kieslich Klaus , Ernst Ludger
Published: February 2015

The trimethylsilylalkyl acetoacetates 1 b and 2 b as well as their carba analogues 1 a and 2 a have been reduced microbiologically by Kloeckera corticis (ATCC 20109), leading to the corresponding ( + )-3(S)-hydroxybutanoates 3b, 4b, 3a, and 4a. The enantiomeric purity was found to be 80% (3a, 3b, 4b) and 65% (4a), respectively. The reduction of lb and 2b is - to our knowledge - the first example for a controlled microbiological transformation of organosilicon substrates.
Ein Beitrag zur Frage der Existenz von dπpπ-Binduiigsanteilen zwischen Platin und sp2-hybridisierten Kohlenstoff-Atomen in Phenyl-Platin-Verbindungen/ A Contribution on the Existence of dπpπ-Interactions between Platinum and sp2-hybridized Carbon in Phenyl-Platinum Compounds
Authors: Bayer Ulrich , Brune Hans Albert
Published: February 2015

19F NMR chemical shifts of 14 fluorine substituted cis-Bis(phenyl)bis(triphenylphos-phane)platinum(II) compounds are discussed with respect to dπpπ-interactions between platinum and sp2 -hybridized carbon.
Activated Nitriles in Heterocyclic Synthesis: The Reaction of Cinnamonitrile Derivatives with Active Methylene Reagents
Authors: Elgemeie Galal Eldin Hamza , Elees Samier Anwar , Elsakka Ibraheim , Elnagdi Mohamed Hilmy
Published: February 2015

The reaction of substituted cinnamonitrile derivatives with cyanoacetanilide and ethyl acetoacetate is reported. Several new polyfunctional pyridine and pyran derivatives could be synthesised. The structures of the prepared compounds and the mechanisms of their formation is reported.
Notizen: The Absolute Configuration of Julifloridine
Authors: Ahmad Viqar Uddin , Qazi Sabiha
Published: February 2015

The absolute configuration of julifloridine is proposed to be 2 R, 3 R, 6 R through 13C Spectra, 1H NMR Spectra,
Mößbauer-und Röntgenphotoelektronen-spektroskopische Untersuchungen an Berlinerblau-Analoga des Typs Fe[MB(CN)6] / Mößbauer and X-Ray Photoelectron Spectroscopic Studies on Prussian Blue Analogs of the Type Fe[MB(CN)6]
Authors: Inoue Hidenari , Fluck Ekkehard
Published: February 2015

Prussian Blue analogs of the type Fe[MB(CN)6] (MB = Pd and Pt) crystallize in the face-centered cubic system: space group Fm3m-Oh
5, Z = 4. Magnetochemical and Mößbauer spectroscopic measurements have revealed that nitrogen-coordinated iron(II) ions and carbon-coordinated MB(IV) ions are in the high spin state and in the low spin state, respectively, in the temperature range 4.2 to 300 K. Upon the formation of Fe[MB(CN)6] from K2[MB(CN)6], the binding energies of N 1s, Pd 3d5/2 and Pt 4f7/2 increase while the C 1 s binding energy decreases. This tendency could be interpreted in terms of the inductive effect of iron(II) ions attached to the nitrogen end of cyanide ligands.
Iodination of Aniline Using Thallium(III)-trifluoroacetate and Potassium Iodide
Authors: Braun Siegmund L. , Dürrneyer Edith , Jacob Karl , Vogt Wolfgang
Published: February 2015

A new procedure for a specific micro-synthesis of p-iodo-aniline has been developed. It consists of the reaction of aniline with tliallium(III)-trifluoroacetate followed by the iodination with aqueous potassium iodide.
Darstellung und Kristallstruktur von Antimon(V)oxidhydroxid HSb3O8 / Preparation and Crystal Structure of the Antimony(V) Oxide Hydroxide HSb3O8
Authors: Jäger Gerhard , Jones Peter G. , Sheldrick George M. , Schwarzmann Einhard
Published: February 2015

Colourless crystals of HSb3O8 were prepared by hydrothermal methods from Sb2O5. The crystal structure [P2/n, a = 945.6(2), b = 869.1(2), c = 990.9(2) pm, β = 90.25(2)°, Z = 6. R = 0.045] was determined from diffractometer measurements. Distorted SbO6 octahedra are linked through vertices and edges to form a three-dimensional polymer of pseudo-orthorhombic symmetry. The hydrogen atoms could not be located.
Synthesis and Crystal Structure Determination of a λ3 Pλ5 P-Phosphorane of a Novel Type
Authors: Schiebel Hans-Martin , Schmutzler Reinhard , Schomburg Dietmar , Wermuth Ulrich
Published: February 2015

The synthesis of a λ3 P-substituted phosphorane involving direct substitution of a Ph2P group at λ5P by the reaction of a chlorophosphorane with Ph2PSiMe3 is described; the identity of this novel compound is established by NMR and mass spectroscopy, and by a single crystal X-ray diffraction study.
Organometallphosphin-substituierte Übergangsmetallkomplexe, XIX [1] Carbonyl-dinitrosyl-organometallphosphin-eisen-Komplexe / Organometalphosphine-substituted Transition Metal Complexes, XIX [1] Carbonyl Dinitrosyl Organometalphosphine Iron Complexes
Authors: Schumann Herbert , Köhricht Karl-Heinz , Meißner Manfred
Published: February 2015

The reactions of dicarbonyl dinitrosyl iron with tri-tert-butylphosphine, di(feri-butyl)-trimethylsilyl-, -germyl-, -stannyl-phosphine, tert-butyl-bis(trimethylsilyl)-, -(germyl)-, -(stannyl)phosphine, as well as with tris(trimethylsilyl)-, -(germyl)-, and -(stannyl)phosphine result in the elimination of one CO ligand and the formation of the corresponding carbonyl dinitrosyl organometalphosphine iron complexes. The IR, 1H, 31P, 13C, and 119Sn NMR spectra of the new complexes are reported and discussed.