bluuebunny/crossref_metadata_2025 huggingface dataset:
High Catalytic Activity of Vanadium(V) Oxo-polymers for Oxidative Cleavage of Catechol
Authors: Nishida Yuzo , Kikuchi Hideki
Published: March 2015

Some vanadium(V) oxo-polymers such as cis- V2W4O19
4- and V10O28
6- exhibit high catalytic activity for the oxidative cleavage of 3,5-di-t-butylcatechol. A chelated species of catechol to two vanadium atoms has been assumed as an active intermediate based on the spectroscopic results.
Übergangsmetallkomplexe mit Schwefelliganden, XLII. [Mo(NO)(NR2)(dttd)]: Metall—Amido-Komplexe mit rotationsstabilen M—NR2-Doppelbindungen (R = H, Me, Et; dttd2- = 2,3,8,9-Dibenzo-1,4,7,10-tetrathiadecan(2—)); Synthese, Eigenschaften und Röntgenstrukturanalyse/Transition Metal Complexes with Sulfur Ligands, XLII. [Mo(NO)(NR2)(dttd)]: Metal Amido Complexes with Rotationally Stable M—NR2 Double Bonds (R = H, Me, Et; dttd2- = 2,3,8,9-Dibenzo-1,4,7,10-tetrathiadecane(2—)); Synthesis, Properties and X-Ray Structures
Authors: Sellmann Dieter , Pöhlmann Georg , Knoch Falk , Moll Matthias
Published: March 2015

In order to study the properties of sulfur coordinated transition metal centers, [Mo(NO)(Cl)(dttd)] (1) (dttd2- = 2,3,8,9-dibenzo-1,4,7,10-tetrathiadecane(2 -)) was synthesized. It shows no reaction with AgPF6, but it reacts very rapidly even at low temperatures with liquid ammonia and dialkylamines HNR2 (HNMe2, HNEt2) yielding the corresponding amidocomplexes [Mo(NO)(NR2)(dttd)] (R = H 4, Me 2, Et 3). For these reactions an associative mechanism is suggested. X-ray structure analyses of [Mo(NO)(Cl)(dttd)] (1) and [Mo(NO)(NMe2)(dttd)] (2) show the Mo centers to be coordinated pseudo-octahedrally by two trans thiolato S, two cis thioether S atoms and the two cis coligands NO and Cl or NO and NMe: , respectively. Both dialkylamido complexes (R = Me 2, Et 3) show no coalescence of the two N(alkyl) signals in the 1H NMR spectra up to 140 °C, the NH-Signals of 4 coalesce at 70 ± 5 °C (⊿G* = 73 ± 1.5 kJ mol-1). The amido ligands act as σ - π four electron donor ligands such that the Mo center obtains a formal 18 electron configuration and the Mo-NR2 bond represents a Mo = N double bond. This follows from the short Mo-N distance (192.4(8) pm) and the planarity of the N(alkyl) atom of 2 as well as the stability of the Mo - NR2 bond (R = H, M e, Et) with respect to rotation. Since sterical effects can be excluded, the high rotation barriers must be due to exclusively electronic effects.
Trimethylphosphan-stabilisierte Monocyclopentadienylkomplexe des Niobs(III) und Tantals(III)/Trimethylphosphine Stabilized Monocyclopentadienyl Complexes of Niobium(III) and Tantalum(III)
Authors: Alt H. G. , Engelhardt H. E.
Published: March 2015

The reduction of Cp'MCl4 complexes (Cp' = η5-C5H5, η5-C5Me5; M = Nb, Ta) in the presence of excess PMe3, leads to the highly reactive products Cp'M (PMe3)3Cl2. One or two PMe3 ligands of these compounds can be substituted by CO or CO2 toyield Cp'M (PMe3)2(CO)Cl2, Cp'M(PMe3)(CO)2Cl2 and an oxo complex.
Di-trichloracetimid; IR-Spektrum und Kristallstruktur/Di-trichloroacetimide; IR Spectrum and Crystal Structure
Authors: Patt-Siebel Ute , Müller Ulrich , Klinzing Petra , Dehnicke Kurt
Published: March 2015

Di-trichloroacetimide, HN(COCCl3)2. was prepared by the reaction of trichloroacetic acid with trithiazylchloride at 60 °C. The compound was characterized by its IR spectrum as well as by an X-ray structure determination: Space group P 1, Z = 2, 1662 observed independent reflexions, R = 0.034. Lattice dimensions at 17 °C: a = 640.9(2); b = 924.1(3); c = 943.0(2) pm; α = 92.11(2)°; β = 106.53(3)°; γ = 99.02(3)°. The compound forms the Z,Z(trans-trans)isomer. There is no intermolecular hydrogen-bonding.
Polysulfonylamine, XV [1] Synthese von N,N,N′,N′-Tetramesyl-dicarbonsäurediamiden. Cyclisierung von N,N,N′,N′-Tetramesyl-bernsteinsäurediamid zu γ-DimesyIamino-Δβγ-butenolid / Polysulfonylamines, XV [1]. Synthesis of N,N,N′,N′-Tetramesyl Dicarboxylic Diamides. Cyclization of N,N,N′,N′-Tetramesyl Succinic Diamide to γ-Dimesylamino-Δβγ-butenolide
Authors: Blaschette Armand , Linoh Karin , Koch Dietrich , Ernst Ludger
Published: March 2015

N, N, N′, N′ -Tetramesyl dicarboxylic diamides Ms2NC(O)-Q-C(O)NMs2 [Q = (CH2)n with n = 0 (2a), 2 (2b), 3 (2c), 4 (2d); Q = o-phenylene (2e)] were prepared by reacting AgNMs2 (1) with the appropriate dicarboxylic dichlorides in acetonitrile at room temperature (2a, 2 c-2e) or at 0 °C (2b), respectively. Under similar conditions, malonic dichloride undergoes an elimination, forming AgCl, HNMs2 and probably polymeric C3O2. At 20 °C in CH3CN, the succinic acid derivative 2b eliminates one mole of HNMs2 and, by ring closure, yields γ-dimesylamino-Δβγ- butenolide (4a), the first example of a stable γ-amino-Δβγ-butenolide. Treatment of 4a with aqueous NaOH results in the formation of NaNMs2 and sodium succinate. Crystalline 4a is thermally stable at 100 °C; no signs of an isomerization 4a → γ-dimesylamino-Δαγ-butenolide could be detected. Unlike the structurally related α-angelicalactone (4c), whose bromination affords the saturated dibromolactone 9 as a mixture of cis- and mws-isom ers, 4a adds bromine (20 °C, CHCl3) under ring cleavage to form BrC(O)CH2CHBrC(O)NMs2 (7). The new compounds 2, 4a and 7 as well as the stereoisomers of 9 were characterized by spectroscopic (1H and 13C NMR, MS, IR) and analytical methods. In order to obtain reference values for the chemical shifts of 7, the following new compounds were prepared: CH3(CH2)2C(O)NMs2 (10c, from 1 and butvryl chloride); CH3CH2CHBrC(O)NMs2 (12c, from 1 and 2-bromobutyryl bromide); C2H5OC(O)CH 2CHBrC(O)NMs2 (13, from 7 with ethanol and from 4a by simultaneous reaction with bromine and ethanol).
Untersuchungen zur Struktur von Co(III)-und Ni(II)-Komplexen der Pyridin-2,6-di(monothiocarbonsäure) / Structural Investigations of Co(III)-and Ni(II)-Complexes of Pyridine-2,6 -di(monothiocarboxylic Acid)
Authors: Hildebrand Ulrich H. W. , Lex Johann
Published: March 2015

The preparation and structure elucidation of Co(III)- and Ni(II)-complexes of pyridine- 2, 6-di(monothiocarboxylic acid) are reported. The Co ion chelates two of these tridentate ligands to form the octahedral bis(pyridine-2,6-dicarbothioato)-cobaltat(III). whereas the Ni ion coordinates only with two of the three binding sites of each ligand to give a tetrahedral complex. Bis(pyridine-2,6-dicarbothioato)-nickelat(II) is stable only in the absence of O2; it polymerizes by formation of disulfid bridges between the free thiocarboxyl groups if exposed to air.
Reaktionen von N-Lithio-N, N′-di(t-butyl)-S-phenylsulfinsäureimidamid mit Chloriden der Elemente der 4. Gruppe des Periodensystems Struktur des O[TiCl2N2(But)2SPh]2/Reactions of N -Lithio-N ,N′-di(t-butyl)-S -phenylsulfinic Acid Imidamide with Chlorides of the Elements of Group 4 of the Periodic System Structure of O[TiCl2N2(But)2SPh]2
Authors: Roesky H . W . , Mainz B. , Noltemeyer M.
Published: March 2015

N-Lithio-N,N′-di(t-butyl)-S-phenylsulfinic acid imidamide (1) reacts with TiCl4, SiCl4, GeCl4,

SnCl4 and Ph2SnCl2 with monosubstitution at the metal center to yield compounds 2-6. TiCl3N2(But)2SPh (2) slowly hydrolyzes to form O[TiCl2N2(But)2SPh]2 (7). The molecular structure of 7 was investigated by an X-ray structure analysis.
Steroids from Aquatic Organisms, XIX. New Sterols from the Antarctic Sponge Artemisina apollinis
Authors: Seldes Alicia M. , Deluca Mónica E. , Grosa Eduardo G. , Rovirosa Juana , San-Martín Aurelio , Darias José
Published: March 2015

The steroidal composition of the sponge Artemisina apollinis from the Antarctic Ocean was studied by GC-MS and 'H NMR. The sponge contains twenty-eight C 25—C30 derivatives having four different types of nucleus: 3/3-hydroxy-5aH-, 3-keto-5aH-derivatives, 3/3-hydroxy-zl5-and 3/?-hydroxy-zl7-derivatives. Compounds with the first two nucleus are the most abundant, with similar side chain patterns and identical GC profiles. The 3-keto-5aH-derivatives constitute a new group of natural products.
A Convenient Method for the Preparation of (±)Juvenile Hormone III
Authors: Rodriguez Juan B. , Gros Eduardo G.
Published: March 2015

Following a different approach methyl (2 E ,6 E)-farnesoate (4) was prepared in three steps from trans-geranylacetone (1). Compound 4 was regioselectively epoxidized to (±)juvenile hormone III.
Polysulfonylamine, XXI [1]. Bis(dimesylamino)sulfan und Bis(dimesylamino)disulfan: Darstellung, Eigenschaften und Festkörperstrukturen
Authors: Blaschette Armand , Näveke Martina , Jones Peter G.
Published: March 2015

High yield syntheses of the new diaminosulfanes (CH3SO2)2NSN (SO2CH3)2 (1) and (CH3SO2 )2 NSSN (SO2CH3)2 (2) are reported. 1 is obtained by the action of elemental sulfur on (CH3S O2)2NCl and by metathesis of (CH3SO2)2N Ag with SCl2, 2 by the analogous metathesis with S2Cl2. 2 is converted to 1 by partial desulfurization with (C6H5)3 P. 1 and 2 are active transfer reagents of the S2⊕ or S5⊕ group, respectively. Thus, the reaction o f 1 or 2 with n -butanol gives the alkoxysulfanes C4H9OSnOC4H9 (n = 1, 2), and their reaction with [(CH3)3Si]2NH leads to the silylated diaminosulfanes [(CH3)3Si]2NSnN[Si(CH3)3]2 (n = 1, 2). The crystal structures of the title com pounds were determined at - 9 5 °C. The most important features of the structure of 1 are the near planarity of the three bonds around the nitrogen atoms (sum of bond angles 356.9 ), the distances N - SII 169.7 and N -SVI 171.5 pm , and the N - SII -N bond angle o f 105.3° (mean values for two independent molecules). In 2, both nitrogen atoms have a planar geometry (sum of bond angles 360.0°; distance from the plane of their bonded atoms ≤ 2 pm). All N - S bond lengths are approximately equal (mean values: N - SII 170.4, N - SVI 170.7 pm). The S - S bond length is 202.1 pm. The torsion angle N - S - S - N of -8 5 ° lies in the usual range for disulfides X - S - S - Y . For comparison, the known structure of CH3 - N (SO2CH3)2 was redetermined at - 9 5 °C.
Darstellung und Röntgenstrukturanalyse des polymeren Trimethylstannylpertechnetats, {(CH3)3SnOTcO3}n
Authors: Kanellakopulos Basil , Raptis Konstantinos , Nuber Bernhard , Ziegler Manfred L.
Published: March 2015

Reaction of TcO7 with (CH3)4Sn yields besides {(CH3)3SnOTcO3}n (5) also CH 3TcO3 (4) and [(CH3)2 TcO2]2 (3). 5 is not isomorphous with {(CH3)3SnOReO3}n (6), the trimethylstannyl perrhenate, though both compounds have a zickzack chaine structure. 5 is monoclinic (C2h
5-P21/c) with a = 961.6(9), b = 764.5(6), c = 1190.1(7) pm, β = 91.16(7)°, Z = 4, V = 874.71 × 106 pm3, drö = 2.48 g/cm3. While 6 possesses a crystallographic mirror plane 5 does not.
Die Kristallstruktur des Cyanospinells K2Cd(CN)4
Authors: Ziegler Bernd , Babel Dietrich
Published: March 2015

The crystal structure of cubic K2Cd(CN)4 (a = 1286.01(9) pm, Fd 3̅ m, Z = 8) was determined from 175 independent X-ray single crystal reflections (w R = 0.0178). Regular [Cd(CN)4]2- tetrahedra (Cd - C = 222.5(3), C - N = 111.3(3) pm) and strongly trigonally elongated [KN6] octahedra ( K - N = 293.0(2) pm) are arranged in a normal spinel type manner.
{K-[2 2 2]-Crypt}2Se7·H20; Synthese, IR-Spektrum und Kristallstruktur
Authors: Müller Volker , Dehnicke Kurt , Fenske Dieter , Baum Gerhard
Published: March 2015

{K-[2 2 2]-Crypt}2Se7·H20 has been prepared by the reaction of a solution of potassium polyselenide in dimethylformamide at room temperature as black crystals, which were characterized by IR spectroscopy as well as by an X-ray structure determination. Space group P21/n, Z = 4, 5055 observed unique reflexions, R = 0.103. Lattice dimensions at 20 °C: a = 1435(1), b = 1320(1), c = 2966(2) pm, β = 102.50(6)° The heptaselenide ion represents approximately part of a helical chain of polymeric selenium.
Darstellung und Redoxverhalten einer Serie von Cp*/aqua/tripod-KompIexen des Co, Rh und Ru
Authors: Kölle Ulrich , Kläui Wolfgang
Published: March 2015

The following series of complexes [MLL']n+ was prepared: M = Co, Rh, Ru, a) L, L' = η5-C5Me5, b) L, L ' = η5 - C5Me5, H2O, c) L, L' = η5 - C5Me5, tripod (CpCo(P(O)(OEt)2)3
-), d) L, L' = tripod. Redox transitions o f the complexes were investigated by cyclic voltammetry. The results are discussed in terms of ligand field and ligand charge stabilization of the respective electron configurations.
Struktur und X-X-Elektronendichteverteilung in Diaminoboranen des Typs (RCH3N)2BCH3 mit R = H, CH3
Authors: Niederprüm Norbert , Boese Roland , Schmid Günter
Published: March 2015

Using a miniature zone melting device with focused infrared light it was possible to grow crystals of bis(dimethylamino)methylborane (1) and bis(monomethylamino)methylborane (2) at temperatures o f 182 K and 177 K, respectively. The crystal structure and the X - X difference electron density have been determined at temperatures o f 120 K (1) and 115 K (2).

1 crystallizes in the orthorhombic space group Pbca with a = 758.87(7), b = 1559.74(12) and c = 1296.73(12) pm. The mean B - N distance is 143.1(3) pm.

2 crystallizes in the monoclinic space group P21/c with a = 775.06(6), b = 1533.94(17), c = 1011.06(10) pm and β = 102.669(7)° with intermolecular N ··· H hydrogen bridges. The mean B - N distance is 141.5(2) pm.

It is shown that the variation of torsion angles at small angles has more influence on bond lengths than the same or a greater variation at large angles and that it is necessary to pay more attention to the torsion angles ( C - B - N - C ) rather than to the interplanar angles (plane N ,B,N - plane N ,C,C ).
(E)-1,2-Difluoro-1-(pentafluoro-λ6-sulfanyl)- 2-iodoethylene
Authors: Wessolowski Holger , Röschenthaler Gerd-Volker , Winter Rolf , Gard Gary L.
Published: March 2015

The first SF5-substituted perfluoro iodo alkene (E) - F5SCF = CFI was synthesized from the phosphonium salt precursor [(E)-F5SCF = CFPMe3]+BF4
- and iodine.
Synthesen von 1,3-Dithiol-2-on-Derivaten,2-Ethylthio-1,3-dithiolium-tetrafluoroboraten und Thieno[2,3-d]-1,3-dithiol-2-thionen / Synthesis of 1,3-Dithiole-2-one Derivatives, 2-Ethylthio-1,3-dithiolium Tetrafluoroborates, and Thieno[2,3-d]-1,3-dithiole-2-thiones
Authors: Dölling Wolfgang , Vogt Almut , Augustin Manfred
Published: March 2015

Substituted 1,3-dithiole-2-ones 2 a - f are obtained by reaction of 1,3-dithiole-2-thiones 1 a - f with mercuric acetate. The thiones 3 react with triethyloxoniumtetrafluoroborate giving 1.3-dithiolium salts 4 a - h . The cyclocondensation of compounds 3 to thieno[2,3-d]-1,3-dithiole- 2-thiones 6 a - c is described. The first synthesis of 5-methylthio-2-thioxo-1,3-dithiole- 4-carboxylic acid is reported.
Struktur des 2,2,4,4-Tetrakis(trifluormethyl)-1,3-diselenetans / Structure of 2,2,4,4-Tetrakis(trifluoromethyl)-1,3-diselenetane
Authors: Rabe Gerd , Keller Klaus , Roesky Herbert W. , Lagow Richard J. , Pauer Frank , Stalke Dietmar
Published: March 2015

The reaction of hexafluoroacetone with triphenylphosphane selenide proceeds with elimination of triphenylphosphane oxide to yield 2,2,4,4-tetrakis(trifluormethyl)-1,3-diselenetane (1). Crystals of 1 that are suitable for X -ray crystal structure analysis have been obtained by recrystallization from hexane.
Pseudo-Polymerization via Symmetric O -H -O Bonding of the Cobaloximatic Acid, Hydro-trans-Diiodobis(2,3-butanedione dioximato(1-)-N ,N′)cobaltate(III). X-Ray Crystal and Molecular Structure
Authors: Mégnamisi-Bélombé Michel , Bokanjo Robert Parfait Massongo , Nuber Bernhard
Published: March 2015

The structure of hydro-trans-diiodobis(2,3-butanedione dioximato)cobaltate(III), H(CoI2(dmg)2) (dmg- = dimethylglyoximate) has been determined by single crystal X -ray diffraction at ambient temperature. The crystals are monoclinic, space group C 2/c, C8H15CoI2N4O4, Mr = 543.98; a = 15.714(6), b = 7.408(3), c = 13.944(5) Å; β = 107.76(3)°; V = 1545.85 Å3; Z = 4; Dc = 2.34 Mg m -3. The com pound is best visualized as a monobasic acid. The molecules are linked together into two-dimensional network, where linkage parallel to the ac plane is effected by weak intermolecular iodine interactions (I ···I = 3.826 Å), and linkage along the b axis by symmetric intermolecular O - H - O bridges (O - Ointermol = 2.499 Å) involving the acidic protons. Each molecule contains two equivalent intramolecular O - H - O bridges (O ··· Ointrarnol = 2.603 Å). The coordination geometry around Co is a distorted (4+2) octahedron of four chelating equatorial N atoms and two apical iodine atoms. The rectilinear I- Co- I triads are arranged in infinite, faintly zigzagged heteroatomic chains propagating parallel to the ac plane.
Arsenic(III) and Antimony(III) Thionylimides
Authors: Herberhold Max , Triebner Thomas , Chivers Tristram
Published: March 2015

The metathetical reactions of potassium thionylimide, KNSO, with arsenic and antimony halides in acetonitrile solution have been used to prepare two series of arsenic and antimony thionylimides, tBu3-nAs(NSO)n and tBu3-nSb(NSO)n, respectively, (n = 3, 2, 1). The tert-butyl- substituted compounds are moisture-sensitive oils. The half-sandwich hydrido-metal complexes CpM(CO)3H react with tBuAs(NSO)2 in THF solution to give the metallo-arsanes [Cp(CO)3M]As(tBu)(NSO) (M = Cr, M o, W).
Synthese und Kristallstruktur eines 1(λ5),4(λ5)-Diphosphaazulens sowie dreier 1 -Phospha-1,6a-dihydropentalene / Synthesis and Crystal Structure of a 1(λ5),4(λ5)-Diphosphaazulene and of Three 1 -Phospha-1,6a-dihydropentalenes
Authors: Silberzahn Jürgen , Pritzkow Hans , Latscha Hans Peter
Published: March 2015

The reaction of acetylene-bis(phosphonous-bisdimethylamide) (1) with tetraphenyl-cyclopentadienone (2) yields a 1-phospha-1,6a-dihydropentalene (4), which can be sulfurized with CS2 to give the 1-thio-compound 5, and oxidized with H2O2 to give the 1-oxo-compound 6.

With dimethyl-acetylenedicarboxylate (7) an amazingly stable l (λ5),4(λ5)-diphosphapentalene (8) is generated, which reacts further with 7 to yield a l(λ5),4(λ5)-diphosphaazulene (9).

The preparation of the new molecules 4, 5, 6, 9 and the crystal structures of 5 and 9 are reported.
Redox Interaction between Binuclear Mn2(III/IV) Complexes and Binuclear Mn2(II/II) Complexes
Authors: Nishida Yuzo , Nasu Miyuki
Published: March 2015

Spectroscopic and ESR studies have revealed that redox interaction occurs between binuclear Mn2(III/IV) complex, [Mn2O2(2,2′-bipyridine)4]3+ and binuclear Mn2(II/II) complexes, [Mn2(L-py)(CH3COO)2]+ and [Mn2(L-py)Cl2]+, in a dilute acetonitrile solution. Electrochemical data suggest that the chloride ion plays an additional important role in the above reaction.
Liquid Crystalline Azomethines and Polyazomethines Containing Azobenzene and Stilbene Units
Authors: Koßmehl Gerhard , Bahr Jürgen
Published: March 2015

Azobenzene and stilbene derivatives with azomethine and ester groups and polymers of corresponding structures with mesogens possessing three to four aromatic systems in their mesogenic units have been synthesized, characterized and studied for their liquid crystalline properties by DSC measurements and observation by polarizing microscopy.
Preparation and Characterization of F3Te(map) and the Structure of Cl3Te(map) (map = 2-(methylamino)pyridinato)
Authors: Kennepohl Dietmar K. , Schmidt Hans-Georg , Noltemeyer Mathias , Roesky Herbert W.
Published: March 2015

The tellurium -nitrogen compounds Cl3Te(map) (1) and F3Te(map) (2) (map = 2-(methylamino)pyridinato), derived from N -silylated map and the corresponding tellurium (IV) halide, have been prepared and characterized. The crystal structure of 1 reveals a dimeric species with two five-coordinate Te(IV) centers that are bridged by longer Te ··· Cl contacts (356 pm average). Crystal data for 1: triclinic, a = 7.280(1), b = 9.512(1), c = 16.004(2) Å, ɑ = 96.67(1), β = 91.95(1), γ = 105.79(1)°, V = 1057(1) Å3, T = 293 K, space group P1̄, Z = 2. Final R and Rw values for 1 are 0.026 and 0.033, respectively.
Hydrocobaltierung von 1,3-Dihydro-1,3-diborafulven-Derivaten HCo(CO)4/Hydrocobaltation of 1,3 - Dihydro - 1,3 - diborafulvene Derivatives with HCo(CO)4
Authors: Nagy-Magos Zsuzsa , Enders Markus , Pritzkow Hans , Siebert Walter
Published: March 2015

(3)

Hydrocobaltation reactions of 1,3-dibora-4,5-benzofulvene (2) and 1,3-dibora[5]radialene with HCo(CO)4 lead to the complexes tricarbonyl-(η5-4,5-benzo-2-isopropyl-1,3-dimethyl- 2,3-dihydro-1,3-diborolyl)cobalt (4) and tricarbonyl-(η5-isopropenyl-2,5-diisopropyl-1,3-dimethyl-1,3-dihydro-1,3-diborolyl)cobalt (5) in 24% and 5% yield, respectively. The constitution of 4 and 5 follows from the spectroscopic data, and is proven by an X-ray structure analysis of 4. The formation of 5 is accompanied by a 1,5-hydrogen shift in the 1.3-dibora[5]radialene (3).
Übergangsmetallkomplexe mit Schwefelliganden, LXXXI [Ru(NO)('S5')]Br, ein reaktiver Ruthenium-Schwefelligand- Nitrosyl-Komplex: Synthese und Reaktionen mit Azid und Amid/Transition Metal Complexes with Sulfur Ligands, LXXXI [Ru(NO)('S5')]Br, a Reactive Ruthenium Sulfur Ligand Nitrosyl Complex: Synthesis and Reactions with Azide and Amide
Authors: Sellmann Dieter , Geck Michael , Moll Matthias
Published: March 2015

In order to investigate the potential conversion of coordinated NO into N2 ligands at Ru sulfur centers, the cationic Ru nitrosyl complex meso-[Ru(NO)('S5')]Br (1)** was synthesized by template alkylation of [NBu4][Ru(NO)('S2')2]** with (BrC2H4)2S. 1 is reactive towards nucleophiles. Reaction with azide yields N2O, N2 and [Ru('S5')]2 (2), reaction with LiNH2, NH3 and NEt3 leads to C-S bond cleavage in the 'S5' ligand of 1 and to the formation of a Ru nitrosyl vinylthioetherthiolate complex.
Crystal Structures of mer-Cr(pyridine)3(N3)3 and Polymeric NaCr(pyridine)4(N3)4. A Structure Containing μ(1,3) Bridging Azido Ligands between Chromium-and Sodium-Centered Polyhedra
Authors: Goher Mohamed A. S. , Abu-Youssef Morsy A. M. , Mautner Franz A.
Published: March 2015

The structures of mer-Cr(py)3(N3)3 (1) and polymeric NaCr(py)4(N3)4 (2) were determined by X-ray crystallography. Crystal data; 1, C15H15N12Cr, triclinic, space group P1̄, a = 895.3(2), b = 999.1(3), c = 1269.9(5) pm , α = 106.76(3), β = 96.69(3), γ = 116.30(2)°, V = 943.8(6) · 106 pm3, Z = 2 and Rw = 0.038 for 1736 observed MoKα diffractometer data; 2, C20H20N16CrNa, monoclinic, space group C2/c, a = 1561.2(3), b = 1028.8(2), c = 1573.6(4) pm, β = 90.70(2)°, V = 2 527.3(9) · 106 pm3, Z = 4 and = 0.033 for 1272 MoKα diffractometer data.

The coordination around the chromium (III) ion in the discrete molecules of 1 is six-coordinate with mean distances Cr-N(py) of 210.2(4) pm and Cr-N(N3) of 200.8(4) pm. The terminal azido ligands are almost linear and asymmetric, the N-N bonds nearer to the metal (118.8(6) to 120.5(7) pm) being significantly longer than the terminal ones (114.7(7) to 115.5(7) pm). In compound 2, each chromium or sodium cation is six-coordinated by four azido groups and two pyridine molecules. The azido groups act as μ(1,3) bridging ligands between chromium and sodium octahedra to form a three-dimensional network structure. The chromium atoms are trans-coordinated by the pyridine ligands whereas the sodium cations are cis-coordinated.
Flavonoids from Three Ethiopian Species of Premna
Authors: Habtemariam Solomon , Gray Alexander I. , Waterman Peter G.
Published: March 2015

Two novel hepta-oxygenated flavonols have been isolated from the aerial parts of Premna

oligotricha and identified, primarily on the basis of N M R spectroscopy, as 3,5,5'-trihydroxy- 6,7,3',4'-tetram ethoxyflavone (2) and 3,5,7,5'-tetrahydroxy-6,3',4'-trim ethoxyflavone (3). Known flavonoids, with lower levels of oxygenation were obtained from two other Premna

species, P. schimperi and P. recinosa.
Notizen: Cycloadditionsreaktion von Trifluorm ethylisocyanid an Diphenylethin/Cycloaddition Reaction of Trifluoromethyl Isocyanide to Diphenyl Ethyne
Authors: Lentz Dieter
Published: March 2015

The cycloaddition reaction of trifluoromethyl isocyanide to diphenylethyne yields 1,2 -diphenyl- 3,4-bis(trifluoromethyl imino)cyclobutene. 1,2-diphenyl- 3-oxo-4-trifluoromethyl iminocyclobutene is obtained as a by-product resulting from hydrolysis. The structure of 1,2-diphenyl-3,4-bis(trifluoromethyl imino)cyclobutene has been elucidated by X-ray crystal structure analysis.
Reaktionen von Germylenen mit Säureaziden / Reactions of Germylenes with Acid Azides
Authors: Meller Anton , Ossig Günter , Maringgele Walter , Noltemeyer Mathias , Stalke Dietmar , Herbst-Irmer Regine , Freitag Stefanie , Sheldrick George M.
Published: March 2015

A, B

Starting materials are the sterically hindered diazagermylenes and C o f the general formula [R (Me3Si)N]2Ge (R = o-disubstituted aryl or mesityl). A and B react with arylsulfonylazides to give the polymeric N ,N -bis(amino)-N '-sulfonylgermazane derivatives 1 and 2. With phenylazidoformiate, A, B and C yield the corresponding diamino(phenoxy)(isocyanato)- germanium (IV ) derivatives 3 -5, while with N ,N -dimethylcarbamoylazide the impure diamino(dimethylamino)(isocyanato)germanium (IV ) com pound 6 is formed. Reactions of A and B with O ,O -diphenyl-phosphorylazide afford the eight-membered (GeNPO)2 ring compounds 7 and 8
. The substances are characterized by C, H , N analyses, 1 - 8 by their mass spectra, and 3 - 8 by NMR ( 1H, l3C, 29Si, 31P). Characteristic IR group frequencies are given for the isocyanato compounds 3 - 6 . Single crystal X -ray structure analyses are reported for C, 4, 5 and 8 .
Reaktion von N-Trimethylsilyl-N′(N″ -trimethylsilylammodiphenylphosphoranylidenimino) sulfamid mit Wolframoxitetrachlorid und die Struktur von (Cl3WNPPh2N)2 Reaction of N-Trimethylsilyl-N′(N″ -trimethylsilylaminodiphenylphosphoranylidene)sulfamide with Tungstenoxitetrachloride and the Structure of (Cl3WNPPh2N)2
Authors: Roesky H. W. , Raubold T. , Noltemeyer M. , Witt M. , Bohra R.
Published: March 2015

1

The reaction of ClSO2N = PPh2Cl () with NH3 yields H2NSO2N = PPh2NH2 (2).This compound is converted to Me3Si(H)NSO2N = PPh2N(H)SiMe3 (3) by Me3SiNMe2. 3 reacts with WOCl4 under elimination of (Me3Si)2O and ClSO2NH2 to yield the eight-membered ring system (Cl3WNPPh2N)2 (4).The molecular structure of 4 was investigated by an X-ray structure analysis.
cis-trans-Isomerie in 1,5-Diaza-2,4-Diphosphorinan-6-onen cis-trans-Isomerism in 1,5-Diaza-2,4-diphosphorinan-6-ones
Authors: Shevchenko I. V. , Furmanova M. V. , Kukhar V. P. , Schmutzler R.
Published: March 2015

The methylene-bis(dialkylaminochlorophosphines) 2a and 2b react with N,N′-dimethyl- N,N′-bis(trimethylsilyl)urea 1 to give the 1,5-diaza-2,4-diphosphorinan-6-ones, 4a and 4b, each of which exists as two isomers. Sulfuration of 4a and 4b led to the stable derivatives, 5a and 5b, which, with the help of column chromatography, were separated into pure cis- and trans-isomers. The structures were established, based upon NMR-spectroscopic, chemical and analytical data.
Über Verbindungen subvalenter Hauptgruppenmetallkationen mit Dithiolaten, 5. Mitteilung. Die Kristallstruktur von (AsPh4)2[Te(S2C = C(CN)2)2] und ab initio-Berechnungen an [Te(S2C =C(CN)2)2]2- / Compounds of Subvalent Main Group Cations with Dithiolates, Part 5. Crystal Structure of (AsPh4)2[Te(S2C = C(CN)2)2] and ab initio Calculation of [Te(S2C = C(CN)2)2]2-
Authors: Hummel Hans-Ulrich , Fischer Thomas , Moll Matthias , Wolski Alexander , Otto Peter , Dietzsch Wolfgang
Published: March 2015

The crystal structure of (AsPh4)2[Te(S2C = C(CN)2)2] has been determined by X-ray diffrac tion and the electronic structure has been calculated using an effective core potential approach for core electrons of Te and minimal basis-sets for valence electrons of Te and electrons of S, C and N. Te is situated in the center of planar [Te(S2C = C(CN)2)2]2- anions and is coordinated by four sulfur atoms in a trapezoid geometry with Te -S distances of 2.463(4), 2.524(4), 2.819(4) and 2.945(3) Å. The compound crystallizes in the triclinic space group P 1̄ with a = 9.562(5), b = 11.430(6), c = 27.319(20) Å, α = 93.248(2), β = 91.06(2), γ = 112.23(4)° and Z = 2. The trapezoid geometry allows a straightforeward mixing of Te 5 s-and one 5p-orbital giving rise to the formation of sp-hybride orbitals.
Beiträge zur Chemie des Phosphors, 220. [Cp*Si(PH2)PH]2 - ein P- und Si-funktionelles 1,3-Diphospha-2,4-disilacyclobutan / Contributions to the Chemistry of Phosphorus, 220. [Cp*Si(PH2)PH]2 - a P- and Si-Functionalized 1,3-Diphospha-2,4-disilacyclobutane
Authors: Baudler Marianne , Oehlert Wolfgang , Tillmanns Barbara
Published: March 2015

The reaction of Cp*SiCl3 with LiAl(PH2)4 yields the compound Cp*Si(PH2)3 (1) which rearranges in the reaction mixture at room temperature to give the new 1,3-diphospha-2,4-disilacyclobutane (1,3-diphospha-2,4-diseletane) [Cp*Si(PH2)PH]2 (2). Compound 2 could be isolated in pure form and has been fully characterized by spectroscopic methods.
Röntgenographische, elektrische und spektroskopische Untersuchungen an den Palladiumchalkogeniden PdS1-xSex / Roentgenographic, Electrical and Spectroscopic Investigations of the Palladium Chalcogenides PdS1-xSex
Authors: Kliche G. , Köhler J. , Bauhofer W.
Published: March 2015

Silvery reflecting melting cakes of PdS1-xSex (0.0 ≤ x ≤ 1.0) have been prepared by annealing mixtures of Pd, S and Se at 873 K in evacuated quartz tubes. The PdS-type mixed crystals are stable only in the ranges 0.0 ≤ .x ≤ 0.2 and 0.9 ≤ x ≤ 1.0, whereas a new phase appears in the intermediate region. The new phase PdS1-xSex (0.2 < x < 0.9) crystallizes in the space group P42/mbc and Z = 24. Lattice constants are a = 1126.2(7), c = 683.2(7) pm (PdS0.6Se0.4) and a = 1130.8(9), c = 685.4(8) pm (PdS0.4Se0.6). The relationships between the new structure type and the PtS and PdS structure types are discussed.

The infrared reflection spectra of polycrystalline samples of PdS were measured between 10 and 300 K in the frequency range from 30 to 400 cm-1. Both phonons and plasmons contribute to the spectra. The temperature dependence of the plasmon contribution shows an unusual behaviour which is explained by the assumption of a phonon assisted hopping conductivity mechanism at low temperatures and a Drude-like transport at high temperatures. The normal mode which may be involved in the hopping process is proposed from a normal coordinate calculation using a three-parameter short range valence force field model. The electrical transport data are in general agreement with the optical ones. The infrared spectra of the mixed crystals PdS1-xSex (0.2 < x ≤ 1) are discussed.
Hexafluoraceton als Schutzgruppen-und Aktivierungsreagenz in der Aminosäure-und Peptidchemie. Synthese Phosphor-substituierter Sarkosin-Derivate unter Verwendung eines neuen elektrophilen Sarkosin-Synthese-Äquivalents / Application of Hexafluoroacetone as Protecting and Activating Reagent in Amino Acid and Peptide Chemistry. Synthesis of Phosphorus Containing Sarcosine Derivatives via a New Electrophilic Sarcosine Synthone
Authors: Burger Klaus , Heistracher Elisabeth , Simmerl Reinhold , Eggersdorfer Manfred
Published: March 2015

Phosphono-, phosphino-, and phosphinyl-sarcosine derivatives are obtained from 4-bromo-3-methyl-2,2-bis(trifluoromethyl)-1.3-oxazolidin-5-one (8) via M ichaelis-Arbusov reaction.
Zn4FeII
5(PO4)6 ∙ 4H2O : Eine reduzierte und „aufgefüllte“ Variante der Zn2(Zn1-xFex)FeIII(PO4)3 • 2H2O-Struktur / Zn4FeII
5(PO4)6 ∙ 4H2O : A Reduced and „Filled“ Variant of the Zn2(Zn1-xFex)FeIII(PO4)3 • 2H2O Structure
Authors: Schmidt Roswitha , Kniep Rüdiger
Published: March 2015

Single crystals of Zn4FeII
5(PO4)6 ∙ 4H2O were grown by hydrothermal treatment of phosphophyllite (Zn2Fe(PO4)2 ∙ 4H2O) in H2O at 180 °C. The crystal structure (tricl., P1̄; a = 651.6(4) pm, b = 902.7(4) pm, c = 995.4(4) pm, α = 69.01(5)°, β = 78.19(5)°, γ = 75.33(5)°; Z = 1) can be derived from the Zn2(Zn1-xFex)FeIII(PO4)3 ∙ 2H2O structure by reduction of FeIII to FeII and by filling a "structure hole" with an additional FeII.
Ca2[FeN2l und Sr2IFeN2]: Nitridoferrate(II) mit isolierten Anionen [Fe2N4]8- und [FeN2]4-/Ca2[FeN2] and Sr2[FeN2]: Nitridoferrates(II) with Isolated Anions [Fe2N4]8- and [FeN2]4-
Authors: Höhn Peter , Kniep Rüdiger
Published: March 2015

Ca2[FeN2] (monocl., C2/m (No. 12); a = 1093.0(2) pm, b = 496.0(1) pm, c = 684.4(1) pm, β = 121.09(1)°; Z = 4) and Sr2[FeN2] (tricl., P1̄ (No. 2); a = 653.8(1) pm, b = 869.0(2) pm, c = 893.2(2) pm, α = 90.22(2)°, β = 109.45(1)°, γ = 102.30(1)°; Z = 5) were prepared by reaction of mixtures Ca3N2/Fe (Sr2N/Fe) with nitrogen (1 atm) at 850 C. The crystal structure of Ca2[FeN2] contains isolated planar anions [Fe2N4]8-; in the crystal structure of Sr2[FeN2] planar [Fe2N4]8- units are present as well as linear anions [FeN2]4-.
Na2HgS2 und K2HgS2, zwei Thiomercurate mit isolierten Anionen/Na2HgS2 and K2HgS2, Two Thiomercurates with Discrete Anions
Authors: Klepp K urt O. , Prager Karl
Published: March 2015

Na2HgS2 and K2HgS2 were obtained as colourless, tabular crystals by reacting the alkali sulfides Na2S and K2S with red HgS at 970 K. Both compounds are orthorhombic: Na2HgS2, oP40, s.g. Pbca with a = 18.24(2) Å, b = 7.494(5) Å, c = 7.237(5) Å, Z = 8; K2HgS2, oP20, s.g. Pbcm a = 10.697(6) Å, b = 7.958(8) Å, c = 7.272(9) Å, Z = 4. Their crystal structures were determined from four circle diffractometer data and refined anisotropically to conventional R-factors of 0.056 (Na2HgS2) and 0.062 (K2HgS2) for 945 and 485 reflections with F0
2 > 3σ(F0
2), resp. The crystal structures represent new structure types. They are closely related with each other and can be derived from hcp-arrays of the chalcogen-atoms. Characteristic feature is the formation of discrete, almost linear [S - Hs - S]2- dithiomercurate anions with average HgS-bond lengths of 2.31 Å.
Strukturen von Tetramesityldistiban (Mes4Sb2) und Trimesitylstiban (Mes3Sb)/Structures of Tetramesityldistibane (Mes4Sb2) and Trimesitylstibane (Mes3Sb)
Authors: Ateș Mustafa , Breunig Hans Joachim , Ebert Klaus H. , Kaller Rose , Dräger Martin , Behrens Ulrich
Published: March 2015

The crystal structure of tetramesityldistibane consists of isolated Mes4Sb2 molecules in the trans conformation (average distance Sb -C 219 pm, distance Sb -Sb 284.9(1) pm, angles SbC2 97°-100°, Sb2C 92°-109°). In the structure of trimesitylstibane there are stacks of isolated trigonal pyramidal Mes3Sb molecules (average distance Sb -C 218 pm, angles SbC2, 104 -106°).
Darstellung von 1,3,5-Trimethyl-4,6-dioxo-1,3,5,2λ3-triazaphosphinanen; Einkristall-Röntgenstrukturanalyse eines Platin(II)-Komplexes/Preparation of 1,3,5-Trimethyl-4,6-dioxo-1,3,5,2λ3-triazaphosphinanes; Single Crystal X-Ray Diffraction Study of a Platinum(II)-Complex
Authors: Meyer Thomas G. , Jones Peter G. , Schmutzler Reinhard
Published: March 2015

A new synthesis for 2-chloro-1,3,5-trimethyl-4,6-dioxo-1,3,5,2λ3-triazaphosphinane (1) is described. Chlorine-fluorine exchange in 1 by means of sodium fluoride in acetonitrile in the presence of catalytic amounts of a crown ether furnished 2-fluoro-1,3,5-trimethyl-4,6-dioxo-1,3,5,2λ3-triazaphosphinane (2). The synthesis of the bromine and iodine analogues, 3 and 4, by metathesis of 1 with the appropriate trimethylsilyl halides, Me3SiBr and Me3SiI, respectively, is also described. The syntheses of an iron(0)tetracarbonyl complex (5) and of a dichloroplatinum( II) complex (6) are reported. A single crystal X-ray diffraction study was conducted on 6. [P21/c, a = 1161.3(3), b = 1423.2(3), c = 1247.7(3) pm, β = 109.42(2)°, R = 0.028], There are deviations from ideal square planar geometry at platinum. The heterocycles display a flattened boat conformation. A Staudinger reaction of 1 with Me3SiN3 led to the formation of a substituted cyclotriphosphazene.
Elektronentransfer und Ionenpaar-Bildung, 28. ESR/ENDOR-Untersuchungen an Radikalanionen und Kontakt-Ionenpaaren der Naturstoff-Chinone Mitomycin C, Streptonigrin, Entobex® und 10,11-Dioxobrucin/Electron Transfer and Ion Pairing, 28. ESR/ENDOR Studies of Radical Anions and Contact Ion Pairs of the Naturally Occurring Quinones Mitomycine C, Streptonigrine, Entobex® and 10,11-Dioxobrucine
Authors: Bock H. , Hänel P. , Herrmann H.-F.
Published: March 2015

Reduction of naturally occurring para-and ortho-benzoquinone derivatives M to their respective radical anions M·⊖ can be accomplished under largely aprotic conditions either by cautious low-temperature reaction in THF containing an excess of (2.2.2) cryptand at a potassium mirror or by using the "mild" single electron transfer reagent tetrabutylammonium boranate R4N⊕BH4
⊖ in DMF. On addition of soluble alkali tetraphenylborates Me⊕[B(C6H5)4]⊖ , their hitherto unknown radical ion pairs [M·⊖ Me⊕]· and/or triple ion radical cations [Me⊕M·⊖Me⊕]·⊕ form, which might be of biological relevance in molecular carrier and "turn off -turn on" switch processes. On addition of metal perchlorates Me⊕n(ClO4
⊖)n with multiply charged counter cations Me⊕n the respective paramagnetic species [M·⊖Me⊕n]·(n-1)⊕ result. Assuming exclusive one-electron transfer reductions without any redox fragmentation reac­tions, ESR, ENDOR and GENERAL TRIPLE spectra are presented and discussed for the following radical anions and radical ion pairs: mitomycin C (M·⊖ and [M·⊖Mex
⊕]·(x-1)⊕ with Me⊕ = Li⊕, Na⊕), streptonigrine (M·⊖ and [M·⊖Lix
⊕]·(x-1)⊕), Entobex® (M·⊖ and [M·⊖Me⊕n]·(n-1)⊕ with Me⊕n = Li⊕, Na⊕, Cd⊕⊕, (H5C6)2Tl⊕) as well as brucinequinone ([M·⊖ Me⊕n]·(n-1)⊕ with Me⊕n = Li⊕, Cd⊕⊕, Pb⊕⊕, La⊕⊕⊕).
Synthesis and Characterization of Ph3SnO2PX2 (X = Cl, Br) and Et2Sn(O2PCl2)2
Authors: Shihada Abdel-Fattah
Published: March 2015

Triphenyltin dichloro- and dibromo-phosphate have been prepared from the reactions of (Ph3Sn)2O with POCl3 and with POBr3, respectively. The reactions of POCl3 with R2SnO (R = Me, Et) lead to R2Sn (O2PCl2)2 and R2SnCl2. Diethyltin bis(dichlorophosphate) has been also prepared by the treatment of (Et2ClSn)2O with POCl3. The infrared spectra of Ph3SnO2PX2 (X = Cl, Br) and Et2Sn(O2PCl2)2 are found to be consistent with polymeric structures with pentacoordinated tin atoms in Ph3SnO2PX2 and hexacoordinated tin atoms in Et2Sn(O2PCl2)2. The El mass spectra of R3SnO2PCl2 (R = Me, Ph) and R2Sn(O2PCl2)2 (R = Me, Et) are given and discussed.
Studies with Polyfunctionally Substituted Heterocycles: Synthesis of New Pyridines, Naphtho[1,2-b]pyrans, Pyrazolo[3,4-b]pyridines and Pyrazolo[l,5-a]pyrimidines
Authors: Elnagdi Mohamed Hilmy , Elghandour Ahmed Hafiz Husein , Ibrahim Mohamed Kamal Ahmed , Hafiz Ibrahim Saad Abdel
Published: March 2015

A variety of new polyfunctionally substituted pyridines, naphthopyrans and pyrazolopyrimidines were prepared via reacting ylidenemalononitriles with thiophenol, thionaphthol, naphthols and or aminopyrazoles.
Notizen: Gold Complexes with Selenium Ligands, V. Synthesis and Crystal Structure of [(Ph3PAu)2Se(p-C6F4Cl)]+SbF6
-
Authors: Jones Peter G. , Thöne Carsten
Published: March 2015

The binuclear complex [(Ph3PAu)2Se(p-C6F4Cl)]+SbF6
- was prepared from Ph3PAuCl and (p-C6F4Cl)2Se2 in the presence of AgSbF6. The crystal structure shows a short intramolecular gold-gold interaction, which leads to an extreme distortion in the coordination geometry at selenium.
Erste Kristallstruktur eines gemischten Al-Mg-Alkoholates/ First Crystal Structure Determination of an Aluminium Magnesium Alkoxide
Authors: Saßmannshausen Jörg , Riedel Ralf , Pflanz Karl B. , Chmiel Horst
Published: March 2015

In the course of investigations concerning the preparation of spinel ultrafiltration membranes we were able to determine the structure of MgAl2(iPrO)8 (3) in the form of its adduct 3 · 2iPrOH . This precursor is used to produce spinel particles in the nanometer range.
Pressure-Induced Phase Transition of the Alkali Metal Amalgam KHg2
Authors: Beister Heinz-Jürgen , Syassen Karl , Deiseroth Hans-Jörg , Toelstede Dirk
Published: March 2015

Potassium amalgam , KHg2, is a shiny black-purple air-sensitive alloy crystallizing, like RbHg2 and CsHg2, in the CeCu2 structure type, which is an open variant of the AlB2 type. We have investigated the phase stability of KHg2 under pressure by powder X -ray diffraction. At 25 kbar KHg2 undergoes a reversible first order phase transition into the AlB2-type structure. Lattice constants and interatomic distances of the high pressure β-phase phase near the phase transition are close to the values for normal pressure NaHg2 which also crystallizes in the AlB2-type structure. The extremely short K - K distances in the β-phase (dK-K = 3.23 Å) indicate that a major change in charge transfer between K atoms and Hg sublattice is associated with the first-order structural transition, driving the potassium atoms towards a positively charged K+ state.
Die Bestimmung von Wasserstoff in Metallen, Metallhydriden und Hydridhalogeniden/Determination of Hydrogen in Metals, Metal Hydrides and Hydrid Halides
Authors: Eger Roland , Mattausch Hansjürgen , Simon Arndt
Published: March 2015

The hydrogen content in NbH0.177, G d H 2, and the chlorides and brom ides of the type LnXHn (Ln = Y, Gd; 0.67 ≤n≤ 1.00) is determined. The samples are burnt in an oxygen atmosphere and the H2O produced in the combustion process is potentiometrically titrated with an accuracy of ± 3% (Karl-Fischer method).
Reaktive E=C(p–p)π Systeme, XXXIV Addition von Alkoholen oder primären Aminen an Phosphaalkene F3CP=C(F)OR. Neue Trifluormethylphosphane und -phosphaalkene/Reactive E = C( p – p ) π-Systems, XXXIV Addition of Alcohols or Primary Amines to Phosphaalkenes F3CP= C(F)OR . Novel Trifluoromethylphosphanes and Phosphaalkenes
Authors: Grobe Joseph , Le Van Duc , Lange Gudrun
Published: March 2015

The course of the reactions o f fluorophosphaalkenes F3CP = C (F)OR [R = Me (1), Et (2)] with methanol or ethanol strongly depends on the experimental conditions. Thus at 70 °C a mixture of the 2-phosphapropionic acid ester F3CP (H )CO2R [R = Me (3), Et (4)] and trifluoromethylphosphane H2PCF3 is formed [molar ratio: 3 or 4 /H2 CF3 ≈1/1]. If the precursors F3CP (H )CO2R [R = Me (3), Et) are used as starting materials, the reaction with ROH under the same conditions affords 3 and 4, respectively, (90 to 95% yield) with only traces of H2PCF 3. In the presence o f iPr2NH these precursors react with R′OH to give the novel trifluoromethylphosphaalkenes F3CP = C (OR )OR [R /R′: Me/Me (6); E t/E t (7); Me/Et (8)]. With Et2NH , 3 undergoes an addition/elimination process yielding the interesting push/pull system Et2N(F)C = P-CO2Me (5). 1 and 2 react with primary amines R′NH2 (R′= tBu, Me) with stereoselective formation of the fairly labile phosphaalkenes F3CP = C(OR)NHR′ [R /R′: Me/tBu (9), Et/tBu(10), Me/Me (11)] with trans-positions for CF3 and NHR′.The new compounds 3 -11 were characterized by spectroscopic investigations (1H , 19F, 31P, 13C NMR ; IR, MS) and determination of M+ or typical fragment ions [M+ -OR ] by high resolution mass spectrometry.
Darstellung und Eigenschaften von Derivaten des 4,5-Benzo-2,3-dihydro- \ ,3-diborols/ Synthesis and Properties of Derivatives of the 4,5-Benzo-2,3-dihydro-1,3-diborole
Authors: Schulz Hartmut , Deforth Thomas , Siebert Walter
Published: March 2015

Reactions of 1,2-bis(trimethyIstannyl)benzene (4) with bis(dichIoroboryl)methane derivatives (Cl2B)2CHR1 (R1 = H ,Me) lead to the formation of the 4,5-benzo-1,3-dichloro-2,3-dihydro-1,3-diboroles 2a,b.Substitution of chlorine in 2a,b by a methyl group using A1Me3 yields the 4,5-benzo-1,3-dimethyl-2,3-dihydro-1,3-diboroles 2c,d, of which 2c is thermally labile. Complexation of 2c,d with [(C5H5)Co(C2H4)2] did not give the expected sandwich complexes 6c,d, but the formation of the triple-decker 7d was observed. The paramagnetic 7d and the diamagnetic 7d+, obtained by oxidation with Ag+BF4
-, were studied by 1H NMR .
Die Kristallstruktur der Verbindung N-Trimethylsilyl-3,4-Dimethylpyridiniumbromid/The Crystal Structure of N -Trimethylsilyl-3,4-dim ethylpyridinium Bromide
Authors: Hensen Karl , Wagner Peter
Published: March 2015

Trimethylbromosilane and 3,4-lutidine form a 1:1 compound which is stable at room temperature. Single crystals of this compound can be isolated by sublimation. It crystallizes in the orthorhombic space group P 2121,21, with lattice constants a = 737,08(9) pm, b = 1295,7(1) pm, c = 1318,8(3) pm. The crystal structure was refined to Rw = 0,042 and proves an ionic structure.
Notizen: Zur Synthese mehrfach borylierter Ferrocene/Synthesis of Polyborylated Ferrocenes
Authors: Wrackmeyer Bernd , Dörfler Udo , Herberhold Max
Published: March 2015

Ferrocene reacts with an excess of boron triiodide or boron tribromide in hexane solution to give mixtures of 1,3,1′-tris- and 1,3,1′,3′-tetrakis- (dihalogenoboryl)ferrocene. The borylation proceeds stepwise, the intermediates being essentially the known dihalogenoborylferrocene and 1,1′-bis- (dihalogenoboryl)ferrocene compounds, although small am ounts of 1,3-bis(dihalogenoboryl)- ferrocene can also be identified. 1H, 11B and 13C NMR data are given.
Darstellung und Kristallstruktur von Rubidiumdicyanoargentat (I), Rb[Ag(CN)2] · 0,4H2O / Synthesis Crystal Structure of Rubidium Dicyanoargentate (I), Rb[Ag(CN)2] · 0,4H2O
Authors: Kühnei Sabine , Range Klaus-Jürgen
Published: March 2015

Rb[Ag(CN)2] · 0,4H2O was synthesized by reaction of silver cyanide with RbOH and liquid HCN at 0 °C. The colourless crystals are orthorhombic, space group Cmc21, with a = 14.440(3), b = 17.645(1), c = 14.799(1) Å and Z = 32. The structure was solved by Patterson and standard direct methods and refined to R = 0.060 and Rw = 0.051, respectively, for 2204 absorption-corrected unique reflections with F > σ(F). The structure comprises slightly buckled layers of linear [Ag(CN)2]- groups, in which silver atoms are arranged in three- and eight-membered rings. The shortest Ag -Ag distance is 3.05 Å. The rubidium ions are arranged in trigonal-prismatic, cubic and square-antiprismatic sites. Additional cavities contain the water molecules.
Binuclear Fulvalene and Bis(cyclopentadienyl)methane Halfsandwich Complexes of Manganese and Rhenium Containing Tetrahydrothiophene Ligands. X-Ray Structure Analysis of {(CO)2Mn[C5H4-C5H4]Mn(CO)2}(μ-SC4H8)
Authors: Herberhold Max , Biersack Martin , Bitterwolf Thomas E. , Rheingold Arnold L.
Published: March 2015

The photo-induced substitution of carbonyl ligands in the binuclear cyclopentadienyl-type complexes (CO)3M[C5H4(CH2)nC5H4]M(CO)3 (n = 0 (fulvalene), M = Mn (1) and Re (2); n = 1 (bis(cyclopentadienyl)methane), M = Mn (3) and Re (4)) has been studied in the presence of tetrahydrothiophene, SC4H8 (tht). Photodecarbonylation of 1 - 4 in tetrahydrofuran solution leads to solvent-stabilized intermediates which react with tht in the dark to give monosubstituted derivatives (CO)3M[C5H4(CH2)nC5H4]M(CO)2(tht) (1a - 4a). In the case of M = Mn, thtbridged compounds {(CO)2Mn[C5H4(CH2)nC5H4]Mn(CO)2}(μ-tht) (n = 0 (1b) and n = 1 (3b)) are also obtained which are the exclusive products of the photolysis of 1 and 3 in benzene in the presence of tht. Photodecarbonylation of 1 - 4 in neat tetrahydrothiophene produces disubstituted derivatives in the case of manganese, (tht)(CO)2Mn[C5H4(CH2)nC5H4]Mn(CO)2(tht) (n = 0 (1c) and n = 1 (3c)), whereas only the monosubstituted complexes 2a and 4a could be isolated in the case of rhenium. The molecular structure of the tht-bridged fulvalene complex 1b has been determined by an X-ray structure analysis. A special reaction of dimethyl disulfane with the photolyzed tetrahydrofuran solution of 2 leads to the bis(methylthiolato) compound (CO)3Re[C5H4- C5H4]Re(CO)(SMe)2 (5). The new complexes were characterized by their IR spectra v(CO) and their 1H and 13C NMR spectra.
Synthese, Flüssigkristallinität und Photochemie von Di- und Tristyrylbenzolen mit Alkoxyseitenketten / Synthesis, Liquid Crystals and Photochemistry of Di- and Tristyrylbenzenes with Alkoxy Side Chains
Authors: Zerban Georg , Meier Herbert
Published: March 2015

The all-(E)-configurated distyrylbenzenes 4a - g and 1,3,5-tristyrylbenzenes 6a,b,g were prepared by stereoselective condensation reactions of azomethines 2 and methylarenes 3 and 4, respectively. 4a,b,d and e generate light sensitive liquid crystals due to the incorporation of calamitic stilbenoid mesogens (chromophores). The photochemistry leading to the degradation of the LC phases and the photochemistry in solution were investigated with regard to (reversible) E/Z isomerization, cyclodimerization and polymerization. For a comparison {E,Z)-4e was prepared in a multistep sequence and photolyzed.