bluuebunny/crossref_metadata_2025 huggingface dataset:
Some New One-dimensional Compounds: Preparation and Optical Properties
Authors: Layek D. , Papavassiliou G. C.
Published: February 2015

New mixed-valence compounds of the type K2[Pt(NH3)X3]-[Pt(NH3)X5] (where X - Cl or Br) were prepared by partial oxidation-addition of K[Pt(NH3)X3] with Cl2 and Br2. The absorption and polarized reflectance spectra of these compounds show a semiconductor behaviour in one dimension and the resonance Raman spectra indicate the ···Pt(II) ···X -Pt(IV)-X chain.
KHgAs (Sb) und KZnAs - Ternäre Verbindungen mit modifizierter Ni2In-Struktur/ KHgAs (Sb) and KZnAs - Ternary Compounds in a Modified Ni2In-Structure
Authors: Vogel Rainer , Schuster Hans-Uwe
Published: February 2015

The compounds KHgAs, KHgSb and KZnAs were prepared and their structures determined by powder and single crystal data. The compounds crystallize in a modified Ni2In-type structure, space group P63/mmc-D4
6h. The cell parameters are:

KHgAs a = 450.6pm, c = 997.6pm, c/a = 2.21;

KHgSb a = 478.4pm, c = 1022.5pm, c/a = 2.14;

KZnAs a = 423.0pm, c = 1023.4pm, c/a = 2.42.
Chemie polyfunktioneller Liganden, 57 [1] Über Iridium(I)- und Platin(II)-Komplexe des Bis(diphenylphosphino)amins und die oxidative Addition kleiner Moleküle an Di[bis(diphenylphosphino)amin-P.P']iricUum(I)-chlorid / Chemistry of Polyfunctional Ligands, 57[1] About Iridium(I) and Platinum(II) Complexes of Bis(diphenylphosphino)amine and the Oxidative Addition of Small Molecules to Di[bis(diphenylphosphino)amine]iridium(I)-chloride
Authors: Ellermann Jochen , Mader Leo
Published: February 2015

R2PNHPR2 (1) (R = C6H5) reacts with [(μ-Cl)Ir(C8H12)]2 in a molar ratio of 4:1, to give the square planar, ionic complex [Ir(R2PNHPR2)2]Cl (2a). By reaction of 2a with NaBR4, [Ir(R2PNHPR2)2]BR4 (2b) is obtained. Treatment of 2 a with CO gives [Ir(CO)(R2PNHPR2)2]Cl (3a). The complex 3a is also formed by the reaction of 1 with Ir(CO)(PR3)2Cl (R = C6H5) and Ir(CO)2(p-H2N-C6H4-CH3)Cl. 3a undergoes metathesis with NH4PF6 to yield [Ir(CO)(R2PNHPR2)2]PF6 (3b). The N-deuterated derivative [Ir(CO)(R2PNDPR2)2]Cl (4) is made by H/D exchange from 3a with CH3OD. Oxidative additions of O2 , CS2, I2 and (SCN)2 to 2a yield [Ir(O2)(R2PNHPR2)2]Cl (5), [Ir(μ2-CS2)(R2PNHPR2)2]Cl (6), [Ir(I)2(R2PNHPR2)2]Cl (7) and [Ir(SCN)2(R2PNHPR2)2]Cl (8). Additionally K2[PtCl4] and 1 reacts to [Pt(R2PNHPR2)2]Cl2 (9). The new compounds are characterised, as far as possible, by their IR, FIR, Raman and 31P NMR spectra.
Organische Schwefelverbindungen, XLVII [1] Dimerisierung des Monothiobenzils zu einem 1.3-Dithietan und dessen Cycloreversion / Organic Sulfur Compounds, XLVII [1] Dimerization of Monothiobenzil to a 1,3-Dithietane and its Cycloreversion
Authors: Bäk Claudia , Praefcke Klaus
Published: February 2015

The thermal dimerization of monothiobenzil (1c) to a 1,3-dithietane (2c) and the photochemical cycloreversion of this heterocycle to 1 c is described.
Di-(2-hydroxy-1 -phenazinyl)methan - eine Verbindung neuartiger Struktur aus Pseudomonas aureofaciens [1] / Di-(2-hydroxy-l-phenazinyl)methane - A Compound of Novel Structure from Pseudomonas aureofacien
Authors: Neuenhaus W. , Römer A. , Budzikiewicz H. , Korth H. , Pulverer G.
Published: February 2015

Di-(2-hydroxy-1-phenazinyl)methane, Phenazines, Bacterial Constituents, Pseudomonas aureofaciens The structure elucidation of di-(2- hydroxy-l-phenazinyl)methane from Pseudomonas aureofaciens is described. In addition to the phenazine derivatives isolated earlier from this bacterium 2,3,4-trihydroxyphenazine.
Einkristalldaten der Hochdruck- Hochtemperaturphase von BaGe2 / Structural Refinement of the High Pressure - High Temperature Phase of BaGe2
Authors: Evers Jürgen , Oehlinger Gilbert , Weiss Armin
Published: February 2015

A single crystal investigation of the high pressure - high temperature phase of BaGe2 (α-ThSi2 type of structure) has been performed. Space group I41/amd has been derived from rotation, Weissenberg and precession photographs. On a four-circle-diffractometer 1082 reflections with 0 ≤ h ≤ 8, 0 ≤ fc ≤ 8, 2̅4̅ ≤ l ≤ 24 have been measured with filtered Mo-radiation. This results in 296 independent reflections. Data of the complete structural analysis are summarized in Tabs. I and II. The final R-values are R = 6.09%, Rw= 4.19%, Rg = 4.95%.
(H3O)[Al3(H2PO4)6(HPO4)2] · 4 H2O - ein 2
∞ Al-O-P vernetztes Phosphat mit Oxoniumionen enthaltenden Hohlräumen / (H3O)[Al3(H2PO4)6(HPO4)2] · 4 H2O - a 2
∞ Al-O-P Linked Phosphate with Hollows Containing Oxonium Ions
Authors: Brodalla Dieter , Kniep Rüdiger
Published: February 2015

The crystal structure of (H3O)[Al3(H2PO4)6(HPO4)2] · 4 H2O contains layers consisting of AIO6 octahedra which share vertices with O2P(OH)2 and O3P(OH) tetrahedra. Within these layers there are vacancies (hollows) which are occupied by H3O+ species. Water molecules are fixed between neighbouring layers by hydrogen bonds.

The identity of some other related phosphates is discussed with respect to the crystal structure described in this paper.
A Comment on the Paper “Benzo-lλ4, 2-thiazol, a New Bicyclic 10π-System”
Authors: Davis Michael
Published: February 2015

The “novel 10π-system" reported earlier is a 2,1-benzisothiazole, a well-known heterocyclic system.
Electronic Effects of Aryl and Heteroaryl Groups on the Rate of Quaternization of 5-Aryl(or Heteroaryl)pyrimidines
Authors: Allen David W. , Buckland David J. , Hutley Barrie G.
Published: February 2015

The kinetics of quaternization of a series of 5-aryl- and 5-heteroarylpyrimidines with phenacyl bromide in acetonitrile have been studied in order to assess the electronic effects of the 5-substituent. The observed order of reactivity is 5-(1-methylpyrrol-2-yl) > 5-panisyl >5-(2-furyl) >5-p-tolyl > 5-(2-thienyl) >phenyl > 5-(m-chlorophenyl). The reactions are enthalpy controlled and the rate data can be accounted for in terms of the electronwithdrawing or donating ability of the 5-substituent. The substituent effects of the 2-fury 1- and 2-thienyl groups in the above reaction are significantly different from those observed in the piperidinolysis of 2-chloro-5(2-heteroaryl)pyrimidines.
Notizen: Darstellung, Kristallstrukturdaten und Eigenschaften der quaternären Thiostannate(IV) BaZnSnS4 und BaMnSnS4 / Preparation, Crystal Data and Properties of the Quaternary Thiostannates(IV) BaZnSnS4 and BaMnSnS4
Authors: Teske Chr. L.
Published: February 2015

BaZnSnS4 and BaMnSnS4 were prepared for the first time and the atomic positions of the crystal structure were refined. Both compounds crystallize isotypically with BaCdSnS4 [1]. Space group C19
2v-Fdd2 (No. 43) orthorhombic. BaZnSnS4: a = 2196,4; b = 2150,4; c = 1270,1 pm; BaMnSnS4: a = 2173,1; b = 2144,9; c = 1259,1.
Darstellung Diorganylamino-substituierter Carbodiphosphorane [1] / Synthesis of Diorganylamino Substituted Carbodiphosphoranes [1]
Authors: Appel Rolf , Baumeister Ulrich
Published: February 2015

Aminolysis of the P-chlorofunctional carbodiphosphorane Ph3P = C = PPh2Cl (1) affords the diorganylamino substituted phosphonium salts

(3a-e, R = alkyl), which can be dehydrohalogenated in good yield by NaH to give the neutral compounds Ph3P = C - PP2(NR2) (4a-e). The structure of the hitherto unknown amino-carbodiphosphoranes has been confirmed by 31P{1H} and 13C{1H} NMR data as well as by hydrolysis to give 5, hydrochlorination to 6b, e and methylation to 7a, e.
Darstellung und Eigenschaften des Nitrenkomplexes (C5H5)2VNSiMe3 Zur Reaktion von Vanadocen mit Silylaziden [1] / Reaction of Vanadocene with Silyl Azides Preparation and Properties of the Nitrene Complex (C5H5)2 VNSiMe3 [1]
Authors: Wiberg Nils , Häring Heinz-Wolfgang , Schubert Ulrich
Published: February 2015

The silyl azides R3SiN3 (R = Me, Ph) react with dicyclopentadienyl vanadium Cp2V under formation of (Cp2V)2NSiMe3 and Cp2VNSiPh3, respectively. By reaction with Me3SiN=NSiMe3, (Cp2V)2NSiMe3 is transformed into CpVNN(SiMe3)2 and Cp2VNSiMe3 (la). According to X-ray analysis, 1a contains a linear V≡N-Si-group. 1a decomposes under formation of (CpV)2(NSiMe3)3. Reaction of 1a with Me3SnCl leads to [CpVCl(NSiMe3)]2 (two isomers).
Produkte der Umsetzung des Pentacarbonyleisens mit N-substituierten Imidazolen / Products of the Reaction of Pentacarbonyl Iron with N-Substituted Imidazoles
Authors: Seel Fritz , Lehnert Rudi , Bill Eckhard , Trautwein Alfred
Published: February 2015

1-Methyl-, 1-ethyl-, 1,2-dimethyl-and 1,2,3,4-tetramethylimidazole react with pentacarbonyliron to yield [FeIm6][Fe(CO)8] (1), [FeIm6][Fe(CO)4]2 (2), [FeIm4][Fe(CO)4] (3) and Fe(Im)(CO)2 (4) (Im = substituted imidazole). The crystal and molecular structures of 1 and 2 have been determined by X-ray diffraction. For 1 and 2 agreement between calculated and measured Mössbauer absorption intensities was obtained by taking into account Debye-Waller-factors, which were derived from the X-ray diffraction experiments.
Gemischtvalente Oxovanadate, I Ein neuer Strukturtyp für die Verbindung BaV10O15/Oxovanadates with Mixed Valence, I A New Crystal Structure of BaV10O15
Authors: Beaulieu D. Chales de , Müller-Buschbaum Hk.
Published: February 2015

BaV10O15 was prepared by high temperature reaction of BaO and V2O3 in H2-atmosphere (T > 1800°). X-ray investigations of single crystals show a new structure type with octa-hedral coordination of V3+/V2+ (statistical distribution) and cuboctahedral surrounding of Ba2+ . Orthorhombic symmetry, space group D18
2h-Ccmb, a = 995,8; b = 1161,8; c = 941,0; Z = 4.
119Sn-NMR-Verchiebungen und Koordinationsverschiebungen von Halogenstannylenkomplexen/119Sn-NMR Shifts and Coordination Shifts of Halogenostannylene Complexes
Authors: Mont Wolf-Walther du , Kroth Heinz-Jürgen
Published: February 2015

119Sn NMR data of a number of base-stabilized stannylenes L (L = R3P-SnCl2, (THF)xSnCl2, (THF)xSnBr2 are compared with those of the corresponding tin ylid complexes M(CO)5L (M = Cr, W). 119Sn NMR coordination shifts are strongly dependent on the transition metal. Increasing the number of base ligands attached to transition metal-coordinated tin(II) leads to significant upfield shifts and to increasing coupling constants 1J(119Sn183W).
Synthese yon 2.2-Dihydro-1.4.2-diazaphosphol-4-enen [1]/Synthesis of 2,2-Dihydro-1,4,2-diazaphosphol-4-enes
Authors: Burger K. , Penninger S. , Tremmel S.
Published: February 2015

4,4-Bis(trifluoromethyl)-1,3-diazabuta-1,3-dienes below 0 °C react with P(III) compounds to give 2,2-dihydro-1,4,2-diazaphosphol-4-enes. IR, 1H, 19F, 31P NMR, and mass spectra data of the new heterocyclic compounds are discussed.
Alkaloide in Tabernaemontana-Arten, XII [1]. Untersuchung der Alkaloide von Tabernaemontana olivacea — Condylocarpin-N-oxid, ein neues Alkaloid aus T. olivacea / Alkaloids in Tabernaemontana Species, XII [1]. Investigation of the Alkaloids from Tabernaemontana olivacea - Condylocarpine-N-oxide, a New Alkaloid from T. olivacea
Authors: Achenbach Hans , Raffelsberger Bernd
Published: February 2015

From the methanolic extract of the stems of T. olivacea we isolated 12 alkaloids and deduced their structures. The main alkaloidal constituent is the new compound condylo-carpine-Nb-oxide (1). Besides this, we found akuammidine (16) and 10 further known alkaloids, which belong to the ibogamine-type
The Structure of [η3-C3H5PdP(C6H5)3]2
Authors: Jolly P. W. , Krüger C. , Schick K.-P. , Wilke G.
Published: February 2015

The 1:1 adduct formed by triphenylphosphine with bis(η3-allyl)palladium disproportionates at 0 °C in toluene to give the title compound. A crystal structure determination confirms the presence of a Pd-Pd bond and bridging η3-allyl groups
Das Verhalten von Mono- und Diorganylphosphansulfiden gegenüber Metallcarbonylsystemen, XXIII [1]. Kristall- und Molekülstruktur von μ-[Oxybis(dimethylphosphan)] - bis[dicarbonyl(h5-cyclopentadienyl)- mangan(I)] / The Behavior of Mono- and Diorganylphosphane Sulfides towards Metal Carbonyl Systems, XXIII [1]. Crystal and Molecular Structure of μ-[Oxybis(dimethylphosphane)]- bis [dicarbonyl (h5- cyclopentadienyl) - manganese(I)]
Authors: Lindner Ekkehard , Hoehne Sigurd , Gumz Jörg-Peter
Published: February 2015

[h5
-C5H5(OC)2MnP(CH3)2]2O (1) which can be prepared from h5-C5H5(OC)2MnP(CH3)2Cl, H2O and N(C2H5)3, crystallizes monoclinicly in the space group P21/c with two molecules in the unit coll. The crystal structure was refined to a R-value of 0.055. 1 contains disordered bridging O atoms
Schwingungsspektren der käfigstrukturierten Verbindungen P4S3, P4Se3, As4S3 und As4Se3 / Vibrational Spectra of the Cage Compounds P4S3, P4Se3, As4S3 and As4Se3
Authors: Bues W. , Somer M. , Brockner W.
Published: February 2015

The vibrational spectra of the cage compounds P4S3, P4Se3 and AS4S3 have been recorded in the solid and the molten state. The vibrational spectra of crystalline As4Se3, which decomposes during melting, have been investigated. The frequencies wore assigned using the concept of group frequencies.

A new assignment of the Raman frequencies is proposed for P4S3 based on new po­larization data. The frequencies of the arsenic compounds are reported for the first time. The Raman spectra of the molten compounds suggest that the cage structure is retained in the molten state.
Aminofluorsilane: 1.3-Silylgruppenwanderung und gehinderte Si-N-Bindungsrotation / Aminofluorosilanes: 1.3-Migration of Silyl Groups and Si-N-Rotational Barrier
Authors: Klingebiel Uwe , Neemann Jutta
Published: February 2015

Triaminofluorosilanes with bulky amino groups are prepared by the reaction of bis- (organyl-trimethylsilyl)amino-difluorosilanes with lithiated amines. A 1,3-migration of trimethylsilyl groups from bulky alkylamino substituents to arylamino substituents is observed in these reactions. Structural isomers of the new triaminofluorosilanes were isolated. The silyl group migration depends on steric and electronic effects. Further reactions of the triaminofluorosilanes with butyllithium and trifluoroorganylsilanes lead to the formation of difluorosilyl-substituted triaminofluorosilanes and LiF. The symmetric compounds show AB-systems for the fluorine atoms of the difluorosilyl groups in the low temperature 19F NMR Spectra, due to hindered rotation about the Si-N-bond. The coalescence temperature depends on the bulkiness of the substituents and is observed at or about room temperature.
Darstellung von "Nitrenkomplexen" via Säureazide und Azidosäureester / Synthesis of "Nitrene Complexes" via Acid Azides and Azido Acid Esters
Authors: Korswagen Richard , Ziegler Manfred L.
Published: February 2015

The photochemical reaction of carboxylic acid azides and azido carboxylic acid esters, respectively, with η5 -C5H5Mo(CO)3CH3 in CH2Cl2 seems to be a general route to the nitrene bridged complexes η5-C5H5(O =)Mo-μ(O)-μ(NCOR)Mo(= O)-η5 -C5H5 and η5-C5H5(O =)Mo-μ(O)-μ(NCOOR)Mo (= O) - η5-C5H5.
Verteilung und Valenz der Kationen in Spinellsystemen mit Eisen und Vanadium, I Röntgenographische und Mößbauer-spektroskopische Untersuchung des Spinellsystems ZnV2O4-ZnFe2O4 / Distribution and Valence of the Cations in Spinel Systems with Iron and Vanadium, IX-ray Investigation and Mössbauer Spectra of the Spinel System ZnV2O4-ZnFe2O4
Authors: Riedel Erwin , Dützmann Till , Pfeil Norbert
Published: February 2015

The spinel system Zn[FexV2-x]O4 has been prepared by heating mixtures of ZnV2O4 and ZnFe2O4 at 1000 °C. The lattice constants increase linearly with x by 3.6 pm, the oxygen parameters are constant with a mean value u = 0.384s. The parameters of room temperature Mössbauer spectra show that in the whole series V(III) and Fe(III) are present.
Verteilung und Valenz der Kationen in Spinellsystemen mit Eisen und Vanadium, IIRöntgenographische Untersuchung, Seebeck Koeffizienten, Mößbauer-und IR-Spektren der Mischkristallreihen Fe2VO4-ZnV2O4 und Fe2VO4-ZnFe2O4 / Distribution and Valence of the Cations in Spinel Systems with Iron and Vanadium, IIX-ray Investigation, Seebeck Coefficients, Mössbauer and IR Spectra of the Solid Solutions Fe2VO4-ZnV2O4 and Fe2VO4-ZnFe2O4
Authors: Riedel Erwin , Pfeil Norbert
Published: February 2015

The spinel series Fe2VO4-ZnV2O4 and Fe2VO4-ZnFe2O4 have been prepared and investigated. The lattice constants and Mössbauer spectra lead to a distribution of cations which proves that Fe2VO4 is a partially inverse spinel with Fe(II) and Fe(III) on the tetrahedral site. The Seebeck effect is interpreted with a model of both tetrahedral and octahedral conduction based on charge hopping.
Zur Kenntnis farbiger ternärer und quaternärer Zintl-Phasen / Coloured Ternary and Quaternary Zintl-Phases
Authors: Eberz Ursula , Seelentag Werner , Schuster Hans-Uwe
Published: February 2015

Ternary and quaternary, mostly coloured compounds of Au, Pd and Pt, resp., with Li, Mg, Sc and Sn were prepared and structurally investigated. They crystallize in a "filled" Zinkblende type structure (space group F?3m) and can be characterized as ternary or quaternary Zintl-phases. Colours seem to depend on unfilled d-orbitals of Au, Pd or Pt.
Darstellung und Charakterisierung der Tetrabutylammoniumsalze der Tetrahalogenooxotechnetate(V), [TcOCl4]- und [TcOBr4]- / Preparation and Characterization of the Tetrabutylammonium Salts of the Tetrahalooxotechnetates(V), [TcOCl4]- and [TcOBr4]-
Authors: Preetz W. , Peters G.
Published: February 2015

The treatment of (TBA)TcO4 with conc. HCl or HBr at room temperature yields (TBA)[TcOCl4] or (TBA)[TcOBr4], which are nearly insoluble in acidic aqueous solutions, but well soluble in organic solvents. The vibrational spectra indicate C4v symmetry for the complex ions. (TBA)[TcOBr4] shows an unusual resonance Raman effect, as the progression of overtones runs with the B1 TcCL4 stretching vibration instead of the symmetric A1 mode. The coupling of B1 with the first overtone of νTcO gives more intense difference than combination bands.
4(4-Alkyloxybenzoyloxy)-4' -cyanoazobenzole: Eine homologe Reihe flüssigkristalliner Verbindungen mit der ungewöhnlichen Phasenfolge smektisch A-nematisch-smektisch A / 4(4-Alkyloxybenzoyloxy)-4'-cyanoazobenzenes: A Homologous Series of Liquid Crystals Exhibiting the Unusual Phase Sequence Smectic A -Nematic -Smectic A
Authors: Heppke Gerd , Hopf Reinhard , Kohne Bernd , Praefcke Klaus
Published: February 2015

The synthesis and the phase transition temperatures of homologous liquid crystalline 4(4-alkyloxybenzoyloxy)-4'-cyanoazobenzenes with alkyl chain length n = 1-12 and n = 16 are reported. All compounds exhibit smectic A phases; the SA phase region being interrupted by a "re-entrant" nematic phase for alkyl chain lengath n ≥ 9.
Notizen: Ternäre Gamma-Messing Phasen in den Systemen Calcium-MIB(IIB)-Quecksilber / New Ternary Gamma-Brass Phases in the Systems Ca-MIB(IIB)-Hg
Authors: Ban Z. , Pušelj M.
Published: February 2015

A series of new ternary intermetallic compounds of the general composition Ca16M18
IB(IIB)-Hg18 (M = Zn, Cd, Hg, Cu, Ag and Au) has been identified. The X-ray powder diffraction patterns were indexed on a basis of primitive cubic unit cells.

From the X-ray data and density measurements it is concluded that these phases belong to the partially disordered (MIB(IIB) and Hg) gamma-brass structure type D83.
Elektrochemische Synthesen, IV Metallcarbonylverbindungen der Eisengruppe/Electrochemical Syntheses, IV Metal Carbonyl Compounds of the Iron Group Elements
Authors: Grobe Joseph , Schneider Bernd Heinz
Published: February 2015

The electrochemical synthesis of iron, cobalt, and nickel carbonyl compounds from metal acetylacetonates of oxidation state + II or + III and from metal anodes is described, solvent effects and the problem of cluster formation are discussed.
Elektrochemische Synthesen, V Phosphansubstituierte Metallcarbonyle der Eisengruppe/ Electrochemical Syntheses, V Phosphane Substituted Metal Carbonyls of the Iron Group Elements
Authors: Grobe Joseph , Schneider Bernd Heinz
Published: February 2015

The electrochemical synthesis of iron, cobalt, and nickel carbonyl derivatives with phosphane ligands from metal anodes is described.
Über Oxidpnictide: Zur Kenntnis von Ba2Mn2Sb2O und Ba2Mn2Bi2O/On Oxidpnictides: Preparation and Crystal Structure of Ba2Mn2Sb2O and Ba2Mn2Bi2O
Authors: Brechtel Erwin , Cordier Gerhard , Schäfer Herbert
Published: February 2015

The new oxide pnictides Ba2Mn2Sb2O and Ba2Mn2Bi2O crystallize in the hexagonal system (space group P63/mmc) with the following constants:

Ba2Mn2Sb2O: a = 471 ± 1 pm, c = 2004 ± 2 pm, c/a = 4.255,

Ba2Mn2Bi2O: a = 480.3 ± 0.5pm, c = 2009.7 ± 1.0pm, c/a = 4.184.

The Mn and Sb(Bi) atoms form corrugated hexagonal nets. These nets are bridged between the Mn atoms by O atoms to double layers separated by Ba atoms.
Strukturen und Schwingungsspektren des Tetramethylammonium -a -dodekawolframatosilikats und des Tetrabutylammonium-β-dodekawolframatosilikats / Structures and Vibrational Spectra of Tetramethylammonium a-Dodecatungstosilicate and Tetrabutylammonium β-Dodecatungstosilicate
Authors: Fuchs Joachim , Thiele Axel , Palm Rosemarie
Published: February 2015

Dodecatungstosilicates free of crystal water were prepared for the first time by using tetraalkylammonium as cation. The crystal structure of the tetramethylammonium a-dodeeatungstosilicate [N(CH3)4]4SiW12O40 (1) and tetrabutylammonium) β-dodecatungstosilicate, [N(C4H9)4]4SiWi2040 (2) were solved by X-ray diffraction. (1) crystallizes tetragonal in the space group 14̅ with lattice parameters a = 14.642 Å; c= 12.706 Å; (2) orthorhombic, space group P212121 with a = 29.277 Å, b = 22.181 Å and c = 15.381 Å. The differences between the two isomeric heteropolyanions are discussed, especially the distances and angles between the tungsten atoms.

Comparison of characteristic differences in the vibrational spectra permits the identification of the isomeric anions.
Über Cyanohalogenomercurate der Alkalimetalle / On Cyanohalogenomercurates of Alkali Metals
Authors: Thiele Gerhard , Brodersen Klaus
Published: February 2015

The reactions between Hg(CN)2 and HgX2 in aqueous solutions of alkali halides MX (M = Na, K, Rb; X = CN, Cl, Br, I) lead to mixed cyanohalogenomercurates.

Several compounds gained by crystallisation from aqueous solutions were characterized with X-ray, spectroscopic and thermal methods. The crystal structures of NaHg(CN)2Cl · H2O, KHg(CN)2Cl · H2O and RbHg(CN)2Cl · H2O have been determined by X-ray structure analysis with three-dimensional data. The compounds can be characterized as double salts, because the structures consist of Hg(CN)2-units and isolated M+ and Cl- ions. The relationship between these structures and those of the non-hydrated compounds are discussed.
Synthese und Stabilisierung von (Benzoyl-und Pentafluorbenzoyloxy)diphenylphosphan und Vergleich mit den entsprechenden isomeren Aroyldiphenylphosphanoxiden / Synthesis and Stabilization of (Benzoyl-and Pentafluorobenzoyloxy)diphenylphosphane and Comparison with the Corresponding Isomeric Aroyldiphenylphosphane Oxides
Authors: Lindner Ekkehard , Wuhrmann Juan Carlos
Published: February 2015

(Benzoyloxy)-and (pentafluorobenzoyloxy)diphenylphosphanes RC(O)OPPh2 (2a, b) [R = C6H5 (a), C6F5 (b)] can be obtained by reaction of ClPPh2 (1) with NaO2CC6H5 and AgO2CCeF5, respectively [eq. (1)]. Oxidation of 2a with molecular oxygen yields (benzoyl-oxy)diphenylphosphane oxide (3a) [eq. (2)]. The complexes (OC)5CrPPh2OC(O)R (5a, b) are formed by the action of Na2OCC6H5 and AgO2CC6F5, respectively on (OC)5CrPPh2Cl (4) [eq. (3)]. The chemical and spectroscopical properties of the (aroyloxy)diphenylphosphanes (2 a, b) are compared with the corresponding aryldiphenylphosphane oxides.
(η3+ -Benzyl)(η4 -cyclooctadien)rhodium(I)-Komplexe / (η3 -Benzyl)(η4 -cyclooctadiene)rhodium(I) Complexes
Authors: Stühler Hans-Otto , Pickardt Joachim
Published: February 2015

Reactions of [(COD)RhCl]2 (2) (COD = 1,5-cyclooctadiene) with i-C3H7MgBr in ether and styrene or o-methylstyrene lead to formation of the complexes [(COD)Rh(η3 -7-methyl-benzyl)] (3) and [(COD)Rh(η3 -6,7-dimethylbenzyl)] (4), respectively. 4 was characterized by X-ray analysis. With β-methylstyrene or allylbenzene [(COD)Rh(η3 -7-ethylbenzyl)] (5) is formed; the latter case leads to precedent isomerisation of allylbenzene to β-methyl-styrene. On the other hand no η3 -benzylrhodium complexes could be isolated by reactions of 2 with a-methylstyrene, 2,4-dimethylstyrene, 2,6-dimethylstyrene or 2,4,6-trimethyl-styrene. The steric reasons for this behaviour are discussed.
Enhydrazine, XXX [1]. Phenyloge Enhydrazine ohne direkte N.N-Bindung / Enehydrazines, XXX [1]. Phenylogous Enehydrazines without a Direct N,N-Bond
Authors: Sucrow Wolfgang , Turnschek Wolfgang
Published: February 2015

The phenylogous enehydrazines 3 a-c prepared from the three isomeric benzenediamines 1 a - c and dimedone (2) were treated with the acetylenic esters 4a-b. While 3 c did not react under the applied conditions, 3 a, b gave the openchained products 5 a, b, 7 a, b, and 9 and, in one case, the ringclosed N-addition product 6 as well as the C-addition products which, however, cyclized to the corresponding quinoline-2,5-diones 8 a, b and 10. In compound 11 both reaction types were realized.
A Fundamental Study of Quantitative Desulfurization of Sulfur Containing Amino Acids by Raney Nickel and its Character
Authors: Ohmori Shinji , Takahashi Kazuko , Ikeda Mikiko , Ubuka Toshihiko
Published: February 2015

The desulfurization of several naturally occurring sulfur-containing amino acids by Raney nickel was studied under various conditions. Raney nickel, which was prepared by treating Al-Ni alloy with 5 N NaOH at 60 °C for 30 min, and was not washed with water, was most active and desulfurized, in quantitative yield, methionine, homocysteine, homocystine, homocysteine sulfinic acid, S-(2-carboxy-n-propyl)-L-cysteine, cysteine, cystine, cysteine sulfinic acid and S-methylcysteine sulfoxide. Raney nickel prepared from 100 mg of Al-Ni alloy desulfurized quantitatively up to 40 μmol methionine at 60 °C for 30 min. The desulfurization occurred effectively in the pH range of 7 and 13, but not below 7. Methionine sulfone, cysteic acid, and homocysteic acid were not subject to the reaction. The Raney nickel was deactivated by H2S, and H2O2, or combustion. Desulfurization activity was not enhanced by hydrogen gas.
Erste flüssigkristalline Azulen-Derivate [1] / First Liquid Crystal Azulene Derivatives [1]
Authors: Praefcke Klaus , Schmidt Dietmar
Published: February 2015

Various azulene derivatives as a new type of coloured liquid crystals have been synthesized. Their mesomorphic behaviour is described.
Sesquiterpenester der B-Reihe aus Euonymus europaeus L. [1] / Sesquiterpene Esters of Type B from Euonymus europaeus L. [1]
Authors: Romer A. , Thomas H. , Kreuels B. , Budzikiewicz H.
Published: February 2015

The structure of several esters of 8-epi-desoxymaytol has been elucidated.
Beiträge zur Chemie der Trifluormethylseleninsäure, Redoxprozesse im F3-O-SCFnCl3-n-System / Contributions to the Chemistry of Trifluoromethylseleninic Acid, Redox Processes in the F3CSe(O)OSCFnCl3-n System
Authors: Darmadi Alexius , Haas Alois , Tebbe Klaus
Published: February 2015

Reactions of F3CSe(O)OAg with FnCl3-nCSCl (n = 3, 2, 1) give the compounds F3CSeS(O2)CFnCl3-n. These decompose in the range of- 20 °C to 39 °C to F3CSeCFnCl3-n plus SO2. IR, NMR and mass spectra of the newly prepared compounds are presented.
Reactions of (η-C5H5)Co(CO)2 and (η-EtMe4C5)Co(CO)2 with Iodine and Cyanogen Halides, XCN (X = Br OR I)
Authors: Morán Moisés
Published: February 2015

Cyanogen Halides The title compounds react with iodine to give the iodinecarbonyl complexes (η-C5H5)Co(CO)I2 and (η-EtMe4C5)Co(CO)I2. The reactions of the same compounds with the cyanogen halides XCN (X = Br or I) give rise to the formation of mixed cyano-carbonyl complexes (η-C5H5)Co(CO)(CN)X and (η-EtMe4C5)Co(CO)(CN)X (X = Br or I) respectively. The compounds have been characterized by elemental analyses and IR and HNMR spectra.
5-Chlor-5-phenyl-1-oxa-4.6-dithia-5-stannocan, ein diplanarer Übergangszustand bei der Racemisierung der Wanne-Sessel- Konformation in einem 8-Ring [1] / 5-Chloro-5-phenyl-1-oxa-4,6-dithia-5-stannocane, a Diplanar Transition State for the Racemisation of the Boat-Chair Conformation in an Eight-Membered Ring [1]
Authors: Dräger Martin
Published: February 2015

The title compound has been synthesized from PhSnCl3 and the disodium salt of bis(2-mercaptoethyl)ether. The crystal structure has been determined and refined to R - 0.033. The conformation of the eight-membered heterocycle is slightly disordered and represents a diplanar form, which is generally considered the transition state near the saddle point of the energy surface between the two enantiomers of the boat-chair con-formation. The configuration around tin is a trigonal bipyramid with equatorial sulfur atoms, an equatorial phenyl group and with axial atoms Cl and O (transannular distance Sn···O 241 pm).
Metallorganische Lewissäuren, V [1] Reaktionen von Carbonyl-η5-cyclopentadienylmolybdä ntetrafluoroboraten (η5-C5H5)MO(CO)2(L)FBF3 (L=CO, PR3) mit Phosphanen und Alkenen / Organometallic Lewis Acids, V [1] Reactions of Carbonyl-η5-cyclopentadienyl Molybdenum Tetrafluoroborates (η5-C5H5)Mo(CO)2(L)FBF3 (L = CO, PR3) with Phosphanes and Alkenes
Authors: Sünkel Karlheinz , Ernst Herbert , Beck Wolfgang
Published: February 2015

Tetrafluoroborate complexes (η5 -C5H5)Mo(CO)2(PR3)FBF3 have been prepared by hydride abstraction from the corresponding hydrido compounds using Ph3CBF4. The tetrafluoroborate ligand in (η5 -C5H5)Mo(CO)2(L)FBF3 (L = CO, PR3) is easily sub-stituted by phosphanes, cis-and trans-butene(2), a-acetamidocinnamic acid and buta-diene. Nucleophilic addition of HNMe2 to the butadiene complex [(η5 -C5H5)Mo(CO)3 butadiene)]+BF4
- gives the β-aminoacyl chelate compound 7.
NMR-spektroskopische Untersuchungen an Chalkogenverbindungen, II [1]. 125Te-, 77Se-, 19F- und 13C-chemische Verschiebungen von CF3-substituierten Selen- und Tellurverbindungen [2] / NMR Spectroscopic Studies on Chalcogen Compounds, II [1]. 125Te-, 77Se-, 19F- and 13C Chemical Shifts of CF3 Substituted Selenium and Tellurium Compounds [2]
Authors: Gombler Willy
Published: February 2015

77Se chemical shifts of compounds CF3SeX exhibit an extraordinary good linear correlation with Huggins‘ electronegativities of χx. A range of 1051 ppm is covered for χx values between 1.9 and 3.15. Effective electronegativities are derived from the δ(77Se) values. For some compounds unexpected 77Se chemical shifts are found. This indicates an uncommon electronic constitution at selenium. Electron excitation energies are reported for some of the compounds and their importance for the paramagnetic shielding term is discussed. The relative shieldings of the tellurium compounds are analogous to those of the corresponding selenium compounds. In contrast to 77Se, the 19F shieldings of CF3EX compounds (E = chalcogen) depend inversely on the electronegativity of E and X. The 13C chemical shifts do not correlate with the χx values. NMR data of some CF3Se(IV) and CF3Te(IV) compounds are also reported for comparison
Struktur und Schwingungsspektrum des α-Undekawolframatophosphats Na2[N(CH3)4]4HPW11O39 · 7H2O / Structure and Vibrational Spectrum of the α-Undecatungstophosphate Na2[N(CH3)4]4HPW11O39 · 7H2O
Authors: Fuchs Joachim , Thiele Axel , Palm Rosemarie
Published: February 2015

The crystal structure of the compound Na2[N(CH3)4]4HPW11O39 · 7H2O was solved by X-ray diffraction. It crystallizes in the space group C2/m with lattice parameters a= 23.895 Å, b = 11.417 Å, c = 28.930 Å, β= 126.0°.

The distances between the tungsten atoms and the kind of bridging by oxygen atoms prove the α-isomer. The differences between the vibration spectra of α-undecatungsto-phosphate and α-dodecatungstophosphate are discussed
Zum Bildungsmechanismus von Vanadium Nitrosyl-Komplexen aus Hydroxylamin:Reversible, intramolekulare Umwandlung eines Nitrosylliganden in einen Hydroxylamido(1 —)-Liganden / On the Mechanism of the Formation of Nitrosylvanadium Complexes from Hydroxylamine: Reversible, Intramolecular Conversion of Coordinated Nitric Oxide to a Hydroxylamido(1—) Ligand
Authors: Wieghardt Karl , Quilitzsch Udo
Published: February 2015

The kinetics and the mechanism of a reversible, intramolecular conversion of a coordinated nitrosyl ligand into a probably O,N-coordinated hydroxylamido(1-) ligand is reported for the complex anion [V(tha)(NO)(H2O)]- (tha = 1,1′,1″-nitrilo-tris-2-propanol). Mechanisms for the formation of nitrosyl complexes of the type {V-N=O}4 generated from hydroxylamine and complexes of vanadium in the oxidation states + V or + III, respectively, are proposed.
Organometallphosphin-substituierte Übergangsmetallkomplexe, XXVII [1] Reaktionen von Pentacarbonylmangan-und Pentacarbonylrheniumbromid mit Organoelement(rVb)phosphinen / Organometalphosphine-Substituted Transition Metal Complexes, XXVII [1] Reactions of Pentacarbonylmanganese-and Pentacarbonylrheniumbromide with Organoelement(IVb) Phosphines
Authors: Schumann Herbert , Neumann Heinrich
Published: February 2015

The reactions of pentacarbonyl manganese bromide and pentacarbonyl rhenium bromide with di(tert-butyl)trimethylsilyl phosphine, teri-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 either of corresponding bromo-tetracarbonyl(organometalphosphine)manganese or -rhenium complexes or of corresponding octacarbonyl-bis(μ-organometalphosphido)dimanganese or -dirhenium complexes. The IR, NMR, and Mössbauer spectra are reported and discussed.
Stereoisomerie bei 5-Benzylidentetramsäuren / Stereoisomerism of 5-Benzylidenetetramic Acids
Authors: Stachel Hans-Dietrich , Poschenrieder Hermann
Published: February 2015

N-Substituted (Z)-5-benzylidenetetramic acids undergo isomerisation to E/Z mixtures on treatment with acids or methylate.
Zur Chemie des Ingenols, I Ingenol und einige seiner Derivate/ On the Chemistry of Ingenol, I Ingenol and Some of its Derivatives
Authors: Opferkuch H. J. , Adolf W. , Sorg B. , Kusumoto S. , Hecker E.
Published: February 2015

The tetracyclic polyfunctional diterpene ingenol (1) is the prototype of many diterpenoid parent alcohols of the ingenane type. Esters of these parent alcohols occur -partly together with esters of polyfunctional diterpene parent alcohols of the tigliane and daphnane type -as irritant, cocarcinogenic and antineoplastic principles in species of the family Euphorbiaceae (Spurge). Preparation of 1 from latex of Euphorbia ingens E.May as well as of some functional derivatives of 1 are described.
Kohlensäureesterphosphide - Synthese und Reaktionsverhalten/ Carbonic Ester Phosphides - Synthesis and Chemical Behaviour
Authors: Thamm Rüdiger , Fluck Ekkehard
Published: February 2015

Primary phosphanes, RPH2, react with carbonic ester chlorides, ClCOOR′, in the presence of K2C03 to yield the title compounds RPHCOOR′ and RP(COOR′)2 . The NMR data of the novel compounds are presented and discussed. Other physical and some chemical properties are described.
Conformations of Chlorophylls a and a′ and their Magnesium-Free Derivatives as Revealed by Circular Dichroism and Proton Magnetic Resonance
Authors: Hynninen Paavo H. , Sievers Gunnel
Published: February 2015

The electronic absorption (UV/VIS), circular dichroism (CD) and proton magnetic resonance (1H NMR) spectra have been recorded for C-10 epimeric chlorophylls a and a′, pheophytins a and a′ as well as pheophorbides a and a′. Although the epimers in each pair showed virtually identical UV/VIS spectra, their CD spectra were profoundly different and exhibited opposite signs at most wavelengths in the UV region. The differences were interpreted as arising, in part, from different C-10 configurations, and, in part, from conformational alterations induced by the steric strain in the crowded periphery of the macrocycle. The conformational alterations were also clearly indicated by the 1H NMR Δδ-values observed for the α,β and δ methine protons, the C-10 protons and most methyl group protons of the epimers in each pair. This was considered to imply changes in the geometry of the whole macrocycle. The Δδ-values were larger for the Mg-free epimers than for the chlorophyll epimers, which shows that the central Mg-atom makes the macrocycle more rigid. Correlations between the signs of the CD bands and configurations are discussed.
Kernresonanz-Untersuchunghen von 1.2.3-Selenadiazolen/ Nuclear Magnetic Resonance of 1,2,3-Selenadiazoles
Authors: Meier Herbert , Zountsas Johannes , Zimmer Oswald
Published: February 2015

A 1H and 13C NMR spectroscopical study is performed on the basis of 37 1,2,3-selena-diazoles. Besides the discussion of chemical shifts and coupling constants of 1H and 13C, selenium satellites were measured providing 1H77 Se and 13C77 Se coupling constants.
Darstellung und Charakterisierung von Cyclotri(silaselan) (H2Si-Se)3 / Preparation and Characterisation of Cyclotri(silaselane) (H2Si-Se)3
Authors: Haas Alois , Hitze Reiner
Published: February 2015

In benzene HgSe reacts with H2SiI2 at 120 °C to yield a polymer, which on heating in benzene depolimerizes to form (H2SiSe)3. 1H, 29Si, 77Se, NMR, IR and MS data are presented.
Über die Struktur des Tris-[norbornyl-2] methanols / On the Structure of Tris-[norbornyl-2]methanol
Authors: Roth Klaus
Published: February 2015

Tris[norbornyl-2]methanol The structure of the reaction product of the hydroboration oxidation of norbornene is determined by use of carbon-13 NMR spectroscopy. The conformers distribution of the resulting 1:3 mixture of the two stereoisomere 4 and 5 is analysed by addition of the paramagnetic shift reagent Eu(fod)3.
Alkaloide aus Catharanthus roseus-Zellkulturen, II [1] / Alkaloids from Catharanthus roseus Tissue Cultures, II [1]
Authors: Kohl Werner , Witte Barbara , Höfle Gerhard
Published: February 2015

From the extract of Catharanthus roseus tissue cultures 16 different indole alkaloids have been isolated belonging to heteroyohimbane, aspidosperma and iboga types. The structures were deduced by UV, NMR and mass spectrometry.

Ajmalicine (1) and catharanthine (16) were found to be the major constituents, tetra-hydroalstonine (2), akuammigine (3), 3-isoajmalicine (4), pleiocarpamine (6), akuammiline (6), tabersonine (7), 20-hydroxytabersonine (8), lochnericine (9), horhammericine (10), minovincinine (11), vindolinine (12), 20-epivindolinine (13), vindolinine -Nb-oxide (14) and 20-epivindolinine-Nb-oxide (15) could be determined as minor or trace alkaloids.
Umsetzungen von N-Brom-N-Natriumcarbamidaten mit Organometallverbindungen. Synthesen von N-Brom-N-Metallverbindungen des Zinns und Bleis / Reactions of N-Bromo-N-sodiocarbamidates with Metalorganic Compounds. Syntheses of N-Bromo-N-metallo Compounds of Tin and Lead
Authors: Wagner Eleonore , Münch Volker , Jander Jochen , Latscha Hans Peter
Published: February 2015

N-Bromo-N-sodiocarbamidate, Trimethylbromostannane, Triphenylchloroplumbane N-bromo-N-sodiocarbamidate can be prep-ared by the reaction of N-bromo-carbamidate with sodium hydride. The salt, a white crys-talline compound, decomposes above 140 °C. It reacts with (CH3)3SnBr and (C6H5)3PbCl to give the new N-halogeno-N-metallo compounds C2H5OC(o)NBr-Sn(CH3)3 (dec. 104 °C) and C2H5OC(O)NBr-Pb(C6H5)3 (dec. 126 °C).
ABX-Verbindungen mit modifizierter Ni2In-Struktur / ABX-Compounds with a Modified Ni2In Structure
Authors: Tomuschat Christa , Schuster Hans-Uwe
Published: February 2015

Ten new compounds were synthesized. They crystallize with a Ni2In-type structure (space group P 63/mmc-D4
6h). Their magnetic behaviour was investigated in the temperature range from 80 to 290 K.
Molekül- und Kristallstruktur von 1.1-Dimethylsilylentitanocendichlorid, (CH3)2Si(C5H4)2TiCl2 / Molecular and Crystal Structure of l,r-Dimethylsilylene Titanocene Dichloride, (CH3)2Si(C5H4)2TiCl2
Authors: Köpf Hartmut , Pickardt Joachim
Published: February 2015

The molecular structure of the bridged [1]-titanocenophane 1,1'-dimethylsilylene titanocene dichloride, (CH3)2Si(C5H4)2TiCl2, has been investigated by an X-ray structure determination. Crystal data: monoclinic, space group C2/c, Z = 4, a = 1332.9(3), 6 = 988.7(3), c = 1068.9(3) pm, β = 113.43(2)°. The results are compared with the structural dimensions of similar compounds: 1,1'-methylene titanocene dichloride, CH2(C5H4)TiCl2, with the unbridged titanocene dichloride, (C5H5)2TiCl2 and the ethylene-bridged compound (CH2)2(C5H4)2TiCl2
Organoarsan-stabilisierte und -substituierte Chlorostannylene und -germylene / Chlorostannylenes and Chlorogermylenes Stabilised and Substituted by Organoarsanes
Authors: du Mont Wolf-Walther , Rudolph Gero
Published: February 2015

Arsinogermylenes, Arsinostannylenes Tin dichloride and the germanium dichloride dioxane complexes react with tri-£er£-butyl-+ — arsane to give ylide-type 1:1 complexes <-Bu3As-MCl2 (M = Sn, Ge). With di-ter£-butyl-(trimethylsilyl)arsane substitution reactions lead to the formation of chlorotrimethylsilane and the arsino-substituted chlorostannylenes and -germylenes £-Bu2As-MCl. Physical properties of these compounds indicate the presence of associated structures with bridging arsino groups and terminal M-Cl functions.
Radical-Induced Dephosphorylation of Fructose Phosphates in Aqueous Solution+
Authors: Zegota Henryk , von Sonntag Clemens
Published: February 2015

Oxygen free N2O-saturated aqueous solutions of D-fructose-1-phosphate and D-fructose-6-phosphate were y-irradiated. Inorganic phosphate and phosphate free sugars (containing four to six carbon atoms) were identified and their G-values measured. D-Fructose-1-phosphate yields (G-values in parentheses) inorganic phosphate (1.6), hexos-2-ulose (0.12), 6-deoxy-2,5-hexodiulose (0.16), tetrulose (0.05) and 3-deoxytetrulose (0.15). D-Fructose-6-phosphate yields inorganic phosphate (1.7), hexos-5-ulose (0.1), 6-deoxy-2,5-hexodiulose (0.36), 3-deoxy-2,5-hexodiulose and 2-deoxyhexos-5-ulose (together 0.18). On treatment with alkaline phosphatase further deoxy sugars were re-cognized and in fructose-1-phosphate G(6-deoxy-2,5-hexodiulose) was increased to a G-value of 0.4. Dephosphorylation is considered to occur mainly after OH attack at C-5 and C-l in fructose-1-phosphate and at C-5 and C-6 in fructose-6-phosphate. Reaction mechanisms are discussed.
Über die Entstehung von Zuckern und zuckerähnlichen Substanzen aus in Zeolithen absorbiertem Formaldehyd durch UV-Bestrahlung / Synthesis of Sugars and Sugar-Like Products by UV Irradiation of Formaldehyde Absorbed on Zeolites
Authors: Seel Fritz , Schaum Willi , Simon Georg
Published: February 2015

The formation of sugars and sugar-like substances by UV irradiation of formaldehyde adsorbed on zeolites of type A and X has been demonstrated. The conversion inside or outside the matrix and product distribution depend on the type of zeolite.
Darstellung und Eigenschaften von und Reaktionen mit metallhaltigen Heterocyclen, XXIII [1] Untersuchungen zur P=S-heteroanalogen Cyclocotrimerisierung von Alkinen mit Nitrilen bzw. Isocyaniden / Preparation and Properties of, and Reactions with, Metal-Containing Heterocycles, XXIII [1] Investigations on P=S-Heteroanalogous Cyclocotrimerization of Alkynes with Nitriles and Isocyanides, Respectively
Authors: Lindner Ekkehard , Krieg Claus-Peter , Hoehne Sigurd , Rau Axel
Published: February 2015

The dimanganadiphosphadithiacyclohexadiene [(OC)4MnSP(CH3)2]2 (1) crystallizes in the

orthorhombic space group Pbca with Z = 4. Attempts to cyclotrimerize the intermediate

(2) which is obtained from 1 and the alkyne R-C≡C-R (R = CO2CH3), with the isocyanides L = R'NC (R' = t-Bu, C6Hn11, C6H5) yield to the formation of substitution products

(3a-c). An insertion of the isocyanide into the Mn-C-σ-bond of 3a-c could not be observed, even under drastic conditions. In a similar way

(3d) is isolated from 2 and P(C6H5)3. The structures of the compounds 3 a-d are discussed on the basis of their IR, NMR and mass spectra.
Phasenbeziehungen im System Se-SeCl4 und die Kristallstruktur einer metastabilen Modifikation von SeCl4 / Phase Relations in the System Se-SeCl4 and the Crystal Structure of a Metastable Modification of SeCl4
Authors: Born Peter , Kniep Rüdiger , Mootz Dietrich
Published: February 2015

The system Se-SeCl4 contains the intermediate phase SeCl which melts incongruently at −48 °C. The tetrachloride is dimorphous with a stable α-and a metastable ß-modification. The crystal structure of ß-SeCl4 was determined and shown to be an isotype of TeCl4 with tetrameric cubane-like molecules Se4Cl16.
Trimethylsiyl-tetrafluorotellurate(VI) / Trimethylsilyl Tetrafluorotellurates(VI)
Authors: Bildstein Benno , Tötsch Walter , Sladky Fritz
Published: February 2015

The interaction of MesSiCl with eis-and trans-(HO)2TeF 4 and eis-and £ran.s-HOTeF 4 OCH 3 yields eis-and trans-(Me3SiO)2TeF 4 and eis-and <rans-Me3SiOTeF 4 OCH3, respectively, which have been characterized by NMR spectroscopy (125 Te, 29 Si, 19 F, X H). Die Trimethylsilylgruppe ist eine häufig verwen-dete Abgangsgruppe in Reaktionen mit Fluoriden:
Phosphinsubstituierte Chelatliganden, III [1] η5-Cyclopentadienyleisencarbonyl-Koraplexe mit Thiocarbamoylphosphin-, -phosphinsulfid- und -phosphinoxid-Liganden / Phosphine Substituted Chelate Ligands, III [1] η5 -Cyclopentadienyliron Carbonyl Complexes with Thiocarbamoyl-Phosphine, -Phosphine Sulfide and -Phosphine Oxide Ligands
Authors: Kunze Udo , Antoniadis Antonios
Published: February 2015

The reactions of N-silylated and free diphenylphosphino thioformaraides, Ph2PC(S)NRR′ (R = Ph, Me, Et; R′ = Me3Si, H), with CpFe(CO)2l yield, by displacement of one equiva­lent CO, both red-brown P,S-coordinated chelate complexes 1 a-c and green P-coordinated iodo complexes 2a-c. With thiocarbamoylphosphine sulfides, Ph2P(S)C(S)NHR (R = Ph, Me), the S,S′-coordinated chelate complexes 3a, b are obtained. The corresponding phos­phine oxides only form deeply coloured, weak 1/1 adducts 4a, b with CpFe(CO)2l. The course of the nucleophilic substitution of CpFe(CO)2X (X = Cl, Br, I) by N-silyl phosphino thioformamides reveals a significant dependence on the halogen employed. For X = Cl, elimination of RNCS and formation of the cationic diiron complex [CpFe(CO)2]2
_ PPh2
+Cl- (5 a) takes place, whereas for X = Br no reaction occurs at room temperature. Mechanistic reasons for this unexpected behaviour are discussed.
Phosphor-Ylid-Komplexe des Platins / Phosphorus Ylide Complexes of Platinum
Authors: Scherer Otto J. , Jungmann Heribert
Published: February 2015

The interaction of cis/trans-[Pt(PPh3)2(CH2Cl)Cl] (1) with Ph3P gives the ylide complex

cis-[Pt(PPh3)2(CH2PPh3)Cl]Cl (2), which forms cis-[Pt(PPh3)(CH2PPh3)Cl2] (3) on heating in benzene. In CH2Cl2, Ph3P is added again quantitatively with formation of 2. Irradiation of 3 with a 500 W lamp yields cis-Cl2Pt(PPh 3)2 . The ylide complexes 4 and 5 were prepared by treatment of 3 with (Me2N)3P or Ph3As. 3 and Ph2P(CH2)2PPh2 form the chelate ylide complex 6.
Untersuchungen am System primäres Aminophosphan/Tetrachlormethan bzw. Tetrachlorsilan / Investigations in the System Primary Aminophosphane/Tetrachloromethane, and Tetrachlorosilane, Respectively
Authors: Niecke Edgar , Güth Werner , Lysek Manfred
Published: February 2015

Amino-trichloromethylphosphane 2 and -trichlorosilylphosphane 3 are available from the reactions of bis(trimethylsilyl)aminophosphane 1 with tetrachloromethane and tetrachlorosilane, respectively. While compound 2 can be converted into the methylenephosphane 4 by a β-elimination of hydrogenchloride, 3 eliminates silicochloroform to give the diphosphane 6. In contrast to compound 2, the reaction of the sterically more hindered bis(dimethyl-tert-butyl)aminophosphane 7 with tetrachloromethane yields the corresponding secondary aminochlorophosphane 10.