bluuebunny/crossref_metadata_2025 huggingface dataset:
Reaktioneil mit N,N-Bis(trimethylstannyl)trifluormethansulfonamid und die Röntgenstrukturanalyse eines zwölfgliedrigen Schwefel-Stickstoff-Ringes / Reactions with N,N-Bis(trimethylstannyl)trifluoromethanesulfonamide and the X-ray Structure of a Twelve-Membered Sulfur-Nitrogen-Ring
Authors: Roesky Herbert W. , Diehl Manfred , Krebs Bernt , Hein Michael
Published: February 2015

The title compound N,N-bis(trimethylstannyl)trifluoromethanesulfonamide (1) reacts with S2Cl2, SOCl2 and SO2Cl2 in a molar ratio 2:1 to yield the compounds

S2Cl2 a twelve-membered ring 6. These are the largest neutral sulfur-nitrogen rings of coordination number two at the sulfur atoms known to date. 3 reacts with SOCI2 under migration of a methyl group from the tin to a sulfur atom to yield CF3SO2(R3Sn)NS(CH3)NSO2CF3 (7).

2,2,4,4-Tetramethyl-1,3-bis(trifluormethylsulfonyl)cyclodisilazan and 7 are formed by the reaction of 3 with R2SiCl2- The analogous four-membered germanium compound 8 is obtained from 1 and R2GeCl2. While the pyrolysis of 1 yields only the six-membered cyclotristannazan 9, the six-membered germanium analog is only formed in minor amounts. By treating 9 with R3SiCl the ring is decomposed to give 10. A six-membered ring is formed from the reaction of 1 with ClR2SiOSiR2Cl 11. The structure of 6 is discussed in detail. 6 crystallizes in the monoclinic space group C2/c with a = 24.408(5), b = 7.377(2), c = 16.715(3) Å, β = 117.16(3)° and Z = 4. It has a chair conformation which is different from the isoelectronic S12-structure.
Mineralisierung von 14CCl2F2 durch Oberflächenkatalyse / Mineralisation of 14CCl2F2 Catalysed by Active Surfaces
Authors: Bahadir M. , Schmitzer S. Gäb, J. , Körte F.
Published: February 2015

The reaction behaviour of CCl2F2 adsorbed on silica gel and a natural adsorbent (Mecca Sand) was investigated by means of the 14C-labelled compound. While in the dark no conversion of the substance on silica gel was detected, a significant degradation to 14CO2 was observed on the dry sand. The mineralisation (up to 70%) was due to the applied amount of sand. On irradiation with UV light (λ > 290 nm) the 14CCl2F2 adsorbed on silica gel was partially degraded to 14CO2. However, the mineralisation rate of about 1 % was of less importance in comparison to the rate on the dry sand. The results indicate that the mineralisation takes place at “active sites” on the surface.
Kristall- und Molekülstruktur von Tetrakis(4-fluorophenylisonitril)rhodium(I)chloridhydrat und Tetrakis(4-nitrophenylisonitril)rhodium(I)chlorid / Crystal and Molecular Structure of Tetrakis(4-fiuorophenylisonitrile)rhodium(I) Chloride Hydrate and Tetrakis(4-nitrophenylisonitrile)rhodium(I) Chloride
Authors: Endres Helmut , Gottstein Norbert , Keller Heimo Jürgen , Martin Reinhold , Rodemer Willi , Steiger Wolfgang
Published: February 2015

4-Fluorophenylisonitrile and 4-nitrophenylisonitrile react with μ-dichloro-bis[dicarbo-nylrhodium(I)] [Rh(CO2)Cl]2 yielding the blue tetrakis(4-fluorophenylisonitrile)rhodium-(I)chloride hydrate (1) and the dark green tetrakis(4-nitrophenylisonitrile)rhodium(I) chloride (2). Yellow Perchlorates 3 (of 1) and 4 (of 2) can be obtained from both compounds. 1 crystallizes in the monoclinic space group P 21/c with a - 10.57(2) Å, b = 11.459(5) Å, c = 23.71(5) Å, β = 107.14(4)°, Z = 4. Compound 2 crystallizes in the triclinic space group P1̄ with a = 12.34(4) Å, b = 10.704(3) Å, c = 13.703(3) Å, α = 106.58(2)°, β = 106.07(4)°, γ = 108.29(3)°, Z = 2. 3 belongs to the rhombic space group Pnmm or Pnm2 with a = 11.523(4) Å, b= 15.48(1) Å, c= 15.915(9) Å, Z = 4 and 4 is triclinic with a = 6.987(4) Å, b = 14.300(7) Å, c == 16.983(7)1, α = 71.89(3)°, β = 89.20(4)°, γ = 79.54(4)°, Z = 2.

The structures of 1 and 2 were determined by Patterson and Fourier methods from diffractometer data and refined by least squares to R - 0.062 (1) or R = 0.157 (2). Crystals of both compounds contain metal-to-metal bonded dimers with a Rh-Rh bond distance of 3.207(2) Å in 1 and 3.25(1) Å in 2. the ligands of the two adjacent complex units taking an eclipsed position. These dimers are arranged in layers. There is a second type of layer in 1 containing the water molecules which are hydrogen bonded to the chloride counterions. The blue color of 1 is caused by a strong absorption at 16700 cm-1 (597 nm). 2 has a similar absorption band at 16500 cm-1 (606 nm). Compounds 3 and 4 contain the monomeric complex units.
Zustandsdiagramme der Systeme K2S-Tl2S und Rb2S-Tl2S / The Systems K2S-Tl2S and Rb2S-Tl2S
Authors: Gehle Egbert , Sabrowsky Horst
Published: February 2015

The hexagonal red compound K4Tl2S3 (a - 1060, c = 711.0 pm; Z = 2) and the monoclinic red K7TlS4 (a = 1225, b = 1646, c = 1408 pm, β = 103.2°; Z = 8) were found in the system K2S-Tl2S by DTA and X-ray investigation; Rb4Tl2S3 (hexagonal with a = 1074 and c = 767.4 pm; Z = 2) is the only compound in the system Rb2S-Tl2S.
Derivatives of cis-NPCl2(NSOCl)2 and (NPCl2)2NS0Cl, Part XIII [1] Methyl- and Ethylamino Derivatives of the Ring System cis-NPCl2(NSOX)2 with X = Chlorine and Fluorine
Authors: Cnossen-Voswijk C. , van de Grampel J. C.
Published: February 2015

Aminolysis of cis-NPCl2(NSOX)2, with X = Cl or F, by MeNH2 and EtNH2 proceeds via a geminal substitution pattern. Preparation of the mono-and disubstituted derivatives is described, the NMR data are discussed.
Die Verbindungen Mg(Hacac)2(ClO4)2 und Ca(Hacac)2(ClO 4)2 / The Compounds Mg(Hacac)2(ClO4)2 and Ca(Hacac)2(ClO 4)2
Authors: Kraft Hans G. , Rode Bernd M.
Published: February 2015

The preparation of two new alkaline earth metal complexes with acetylacetone, where the latter acts as a ligand in its diketoform, is described. The solid compounds are characterized by elemental analysis, IR spectra and X-ray diffraction patterns.
Vier- und fünfgliedrige Phosphorheterocyclen, XXXVIII [1] Azaphospholo-benzoxazaphosphole - Synthese, Prototropie und Struktur / Four- and Five - membered Phosphorus Heterocycles, XXXVIII [1] Azaphospholo-benzoaxazaphospholes - Preparation, Proton Shift and Structure
Authors: Schmidpeter Alfred , Weinmaier Josef Helmut
Published: February 2015

The o-hydroxyanile of cinnamic aldehyde reacts with methyl, phenyl, oxy-, and aminochlorophosphanes in a combined substitution and oxidative addition to give phosphoranes with the above mentioned bicyclic structure containing phosphorus as bridgehead. For the aminosubstituted species the reaction is followed by a 1.3 proton shift in the C3 moiety from the cinnamic aldehyde.

Whether the bicyclic system occupies meridional of facial positions of the phosphorus trigonal bipyramid is shown to depend on the nature of the phosphorus substituents. An X - ray structure determination of a tricyclic derivative with axial annelation shows the deviation from the ideal trigonal bipyramidal geometry to lie on the Berry pseudorotion pathway
Struktur eines Spirobi(cyclophosphazens) [1] / Structure of a Spirobi(cyclophosphazene) [1]
Authors: Schmidpeter Alfred , Eiletz Heinz
Published: February 2015

Proton addition to the spirobi(cyclotriphosphazene) anion 1 gives the neutral species 2. An X-ray structure determination shows the proton to be located at a nitrogen atom next t o the spirocenter. The structural consequences of this protonation can be demonstrated by comparisons of intramolecular bond distances and angles and can be understood in terms of structure-determining repulsive N/N interactions in the central PN4 unit
Synthese und Charakterisierung der Spezies R–C7H7Cr(CO)3 mit R = CH3COCH2-, CH3CO(CH3)CH-, CH3COCHCH(CH3)2– / Synthesis and Characterization of the Species R-C7H7Cr(CO)3 with R = CH3COCH2-, CH3CO(CH3)CH - , CH3COCHCH(CH3)2–
Authors: Zahedi Farhad , Ziegler Manfred L.
Published: February 2015

The species R-C7H7Cr(CO)3 (R = -CH2COCH3 , -CH(CH3)COCH3 , -CH(CH)CH3)2COCH3) have been synthesized by reaction of [η7-C7H7Cr(CO)3][BF4] with suitable ketones in the presence of bases like OH- and F- , suggesting a nucleophilic addition of the enolate ion to the cycloheptatrienyl ligand. 1H NMR spectra revealed the CH3-CO-CH(CH3) group being bonded to the cycloheptatriene ligand via the a-carbon atom of the ethyl group
Tetrakis(trimethylsilyl)distiban / Tetrakis (trimethylsilyl) distibane
Authors: Breunig Hans Joachim , Breunig-Lyriti Vassiliki
Published: February 2015

Tetrakis(trimethylsilyl)distibane, (Me3Si)4Sb2 is produced by reaction of tris(trimethylsilyl) stibine, (Me3Si)3Sb, with three or less than three equivalents of t-butyl iodide, with trimethyliodosilane, Me3SiI and iodine. The reaction of (Me3Si)3Sb with three or more equivalents of i-butyl iodide and methyl iodide also yields tri-t-butylstibine, trimethylstibine and Me3SiI
Darstellung und Kristallstruktur von Rb2AgAu3I8, ein Beitrag zur Kristallchemie des einwertigen Silbers und Golds / Preparation and Crystal Structure of Rb2AgAu3ls, a Contribution to the Crystal Chemistry of Monovalent Silver and Gold
Authors: Werner Walther , Strähle Joachim
Published: February 2015

Rb2AgAu3I8 can be prepared in the presence of ether by the reaction of stoichiometric amounts of RbI, AgNO3 and Au with an excess of I2 and concentrated HI. It crystallizes monoclinic in the space group C 2/c. The structure consists of Rb+, Ag+, AuI2- and AuI4 ions. Short distances of 304 pm between the gold(I) atoms can be interpreted by weak bonding interactions. Rb2AgAu3Is shows a very close structural relationship to Rb3Au3Is. The substitution of one third of the Rb+ ions by Ag+ leads only to small changes in the structure, which generate a suitable tetrahedral coordination for the Ag+ ions. The result of the structure determination supports the assumption that the monovalent gold prefers a linear coordination and covalent bonds, whereas silver tends to a more ionic character and higher coordination numbers
Resonance Raman Spectra and Structure of Partially Oxidized Magnus' Salt
Authors: Papavassiliou G. C. , Theophanides T.
Published: February 2015

The partially oxidized form of Magnus' salt has been studied by resonance Raman spectroscopy (RRS) and it has been established that the oxidized form is a chlorine bridged chain polymer. The spectra show intense progressions, υν, where ν, is the symmetric ···X-Pt(IV)-X··· stretching mode, and v the quantum number
Photolysis of Aromatic Ethers
Authors: Benn Reinhard , Dreeskamp Herbert
Published: February 2015

The photolysis of twelve aromatic ethers in solution has been studied by CIDNP and product analysis. The primary step is the scission of the C-O bond in the excited singlet state. The partners of the resulting radical pair (Ph-O' and R1) undergo three major reactions:

(i) geminate recombination and out-of-cage combination resulting in the reformation of the starting material,

(ii) geminate recombination and out-of-cage combination resulting in cyclohexa-2,5- dienones and cyclohexa-2,4-dienones which are isomers of the starting material,

(iii) H-abstraction from the solvent by the more reactive ones of the two radicals (mainly RO") and combination of the less reactive ones {e.g. benzyl) in the bulk solution. The quantum yield of photodecomposition is low for diphenyl ether ( Ø ~ 0.002) but approaches unity (0.3-0.9) in benzyl aryl ethers where the benzyl-oxygen bond is cleaved. If the aroxyl radicals are substituted in ortho (para) position the resulting ortho (para)- disubstituted cyclohexadienones are stable. Otherwise they swiftly rearrange into the phenols. The cyclohexa-2,4-dienones which are the precursors of the ortho-substituted phenols isomerize faster than the cyclohexa-2,5-dienones that give the para-substituted phenols. The rates of these rearrangement reactions are enhanced by acid catalysis
Soluble Polymers for Substitute of Biopolymers in Natural Compounds, I Replacement of the Oligosaccharide Chain in Cinerubin A by Polyoxyethylene
Authors: Geekeler Kurt , Mutter Manfred
Published: February 2015

The glycosidic component of cinerubin A, an anthracycline antibiotic, has been replaced by a polyoxyethylene (POE) chain. The resulting POE-bound e-pyrromycinone was readily soluble in water and exhibited full biological activity
Beiträge zur Chemie des Schwefels, 118 [1] Synthese von Pentathianen und Hexathiocanen / Contributions to the Chemistry of Sulfur, 118 [1] Synthesis of Pentathianes and Hexathiocanes
Authors: Fehér Franz , Glinka Klaus
Published: February 2015

The syntheses of the new compounds dimethylpentathiane, cyclohexylidenepentathiane, dibenzylpentathiane, 1,2,3,5,6,7-hexathiocane, 4,8 -dimethyl-1,2,3,5,6,7 -hexathiocane and bis (cyclohexylidene) -1,2,3,5,6,7 -hexathi - ocane are described. The main mass spectral fragmentation paths are given for both classes of compounds
Darstellung und Kristallstruktur von K3Ag3As2 und K3Cu3As2 / On the Preparation and Crystal Structure of K3Ag3As2 and K3Cu3As2
Authors: Savelsberg Gerhard , Schäfer Herbert
Published: February 2015

Two new intermetallic compounds K3Ag3As2 and K3Cu3As2 have been prepared and their crystal structures determined. They crystallize in the rhombohedral space group R3̅m with

K3Cu3As2: a = 576(2) pm, c = 2026(5) pm,

K3Ag3As2: a = 599(2) pm, c = 2135(4) pm.

and are isotypic to K3Cu3P2
Die Kristallstruktur von Phosphortrichlorid bei –110 °C / The Crystal Structure of Phosphorus Trichloride at –110 °C
Authors: Hartl Hans , Rama Michael
Published: February 2015

A low temperature (-110°C) X-ray structural analysis of PCI3 yielded the bond distances P-Cl = 203.43(12) and 201.86(23) pm and bond angles Cl-P-Cl = 100.04(7)° and 100.19(7)°. The shortest intermolecular contacts P ··· Cl and Cl ···C1 are in the range of the sum of van der Waals-radii
1.3.4.2-Thiadiazaphospholin-2-thione / 1,3,4,2-Thiadiazaphospholine-2-thiones
Authors: Zeiß Werner , Schmidpeter Alfred
Published: February 2015

Perthiophosphonic anhydrides (1) and phos-phorus(V) sulfide react with benzo-phenylhydra-zonoyl chloride (2) eliminating HCl and yielding the title compounds 3 and 4, which formally are cycloadducts of the monomeric units RPS2 and P2S5, respectively, and diphenyl nitrilimine. The corresponding cycloreversion is observed in their mass spectra.
Die Kristallstruktur von (C6H5)4P+IBr2
- / The Crystal Structure of (C6H5)4P+IBr2
-
Authors: Müller Ulrich
Published: February 2015

(C6H5)4P+IBr2
- is isostructural with (C6H5)4As+I3
-, crystallizing in the space group P2/n with a = 1476, b = 767, c = 1025 pm and β = 91.4°. The crystal structure was refined from X-ray diffraction data to a residual index of R = 0.036. The IBr2
- ion is situated on a two-fold rotation axis so that it apparently is symmetrical with I-Br distances of 269.5 pm. Nevertheless, it cannot be excluded that the two I-Br bonds could be as different as 252 and 287 pm with anions randomly adopting one of two orientations
Über die Synthese von siliciumhaltigen anorganischen Heterocyclen aus Phenoxy-thiophosphoryl- und Phenoxy-phosphoryl-dihydrazid / Onthe Synthesisof Silicon Containing Inorganic Heterocycles from Phenoxy-thiophosphoryl-and Phenoxy-phosphoryl-dihydrazide
Authors: Engelhardt Udo , Bünger Thomas
Published: February 2015

Phenoxy-thiophosphoryl-dihydrazide C6H5OP(S)(NH-NH2)2 (1a) and phenoxy-phosphoryl- dihydrazide C6H5OP(O)(NH-NH2)2 (1b) react with tetraalkyl-1,3-dichloro-disiloxanes to give the 1-oxa-3,5-diaza-4-phospha(λ5)-2,6-disila-cyclohexanes 2a-2d. Their 1H NMR, 31P NMR, IR, and Raman data are given
The Chemistry of Heteroarylphosphorus Compounds, Part XIII [1] Some Reactions of 5-(2-Thienyl)dibenzophosphole and its Quaternary Salts
Authors: Allen David W. , Hutley Barrie G.
Published: February 2015

The preparation of 5-(2-thienyl)dibenzophosphole (1) is reported. It readily forms quaternary salts with iodomethane, diiodomethane and benzyl bromide, and also forms a complex with nickel(II) bromide. The methyl- and benzyl-quaternary salts (2, R = Me or PhCH2 ; X = I or Br) undergo hydrolysis with preferential cleavage of the 2-thienyl group, forming the cyclic oxides (3, R = Me or PhCH2). The iodomethyl salt (2, R = CH2I, X = I) undergoes hydrolysis to give a mixture of products, which include the ring-expanded structure (8, R = 2-thienyl). The dibenzophosphole also reacts with ethylpropiolate and water in THF solution with ring-expansion to give the dibenzo[b,d]phosphorin (9)
Synthesis and Biological Activity of Some New Diarylsulphides and Diarylsulphones Containing Amino Acid Moieties, Part I
Authors: Abbady M. A. , Kandeel M. M.
Published: February 2015

4' -Nitro -4-aminodipheny lsulphide (1a) and/or 2'-nitro-4-amino-diphenylsulphide (1b) react with chloroacetylchloride giving 4-chloroacetylamino-diarylsulphides (2a, b) which undergo facile reaction with different amines and hydrazine yielding the 4-glycylamino and 4-hydrazinoacetylaminodiphenylsulphides (3) and (5). Two moles of 2 react with one mole of piperazine and/or hydrazine to give 1,4-Bis(p-N-(p'-nitrodiphenylsulphido)(amino- carbonylmethylene)piperazino (4) and 1,2-Bis(p-N-(o'-nitro-diphenylsulphido)(aminocar- bonylmethylene)hydrazine (6). On condensation of 5 with aromatic aldehydes yielded new Schiff bases (7). Oxidation of 3, 4, 6 and 7 using H2O2/CH3COOH mixtures furnished the corresponding diarylsulphones 8, 9, 10 and 11, respectively. The biological activity of some of the prepared compounds were screened against some strains of bacteria
Reactions of Substituted Xanthotoxin with Nitriles and Hydrazines
Authors: Hishmat . H. , Abd el Rahman A. H. , Gohar A.-K. M. N. , Abdel-Rahman M. H.
Published: February 2015

4-Bromoxanthotoxin reacts with cyanoacetamide to form 4-bromo-o,6-dihydroxantho- toxin, which on hydrolysis with cold hydrochloric acid leads to the formation of cyano- acetic acid derivative, but hydrolysis by boiled hydrochloric acid gives the acetic acid derivative.

Thio-, and 4-nitroxanthotoxin reacts with malononitrile in presence of piperidine by addition to give thio- and 4-nitro-5,6-dihydroxanthotoxin-5-[1',3,,3'-tricyano-2-amino- propene-(2)] respectively, while in presence of ammonia leads to the formation of 5- malononitrile derivatives.

The reaction of hydrazine and phenyl hydrazine with thio- and 4-bromothioxanthotoxin leads to the formation of the hydrazones.

Also thio- and 4-bromothioxanthotoxin reacts with anhydrous aluminium chloride in benzene by cleavage of the furan ring and the formation of 6-(1,2-diphenylethyl)-7,8- dihydroxythiocoumarin and 5-bromo-6-(1,2-diphenylethyl)-7,8-dihydroxythiocoumarin, respectively
Übergangsmetall-Carbin-Komplexe, LI Neue Carben-Komplexe des Mangans durch Umsetzung kationischer Carbin-Komplexe mit Nukleophilen /Transition Metal Carbyne Complexes, LI Novel Carbene Complexes of Manganese by Reaction of Cationic Carbyne Complexes with Nucleophiles
Authors: Fischer Ernst Otto , Besl Gerhard
Published: February 2015

Noveldicarbonyl(π-cyclopentadienyl)-or dicarbonyl (π-methylcyclopentadienyl)-

(methylcarbyne)manganese tetrachloroborates (4 or 4 a)result from the reaction of dicarbonyl(π-cyclopentadienyl)-ordicarbonyl(π-methylcyclopentadienyl)[methoxy(methyl)- carbene]manganese (3 or 3 a)with boron trichloride.The reactions of 4 or 4 a with potassium isothiocyanate and of 4 a with lithium cyclopentadienide lead via nucleophilic attack of the anions to neutral carbene complexes.Dicarbonyl(π-cyclopentadienyl) (phenyl-carbyne) manganese tetrachloroborate (1) reacts with cyanate yielding a isocyanate-(phenyl)carbene complex. Conditions of preparation, properties and spectroscopic investigations are reported.
Einige neue Iridium-Komplexe von Phosphor-yliden /Some New Iridium Complexes of Phosphorus Ylides
Authors: Fraser T. E. , Fuller H.-J. , Schmidbaur H.
Published: February 2015

From the iridium complexes [(1,5-C8H12)IrCl]2, [(C8H14)2IrCl]2 and [(C6H5)3P]2lr(CO)Cl, and the ylides (CH3)3P = CH2 and (CH3)3P = N-P(CH3)2 = CH2, a number of organoiridium compounds has been synthesized. Whereas with (CH3)3P = CH2 the transylidation reaction is very slow and simple addition with formation of sparingly soluble products prevails, the double ylide forms cyclic complexes quite readily. These ylide chelates were characterized by analytical and spectroscopic data.
Resonanz-Raman-Spektrum von Tetrabutylammoniiimoktaiododirhenat(III), [(n-C4H9)4N]2[Re2I8] Resonance Raman Spectrum of Tetrabutylammoniumoctaiododirhenate(III), [(n-C4H9)4N]2[Re2l8]
Authors: Preetz W. , Peters G. , Rudzik L.
Published: February 2015

Irradiation of [(n-C4H9)4N]2[Re2l8] at 80 K with exciting laser lines, which approximately coincide with the electronic band maximum at 520 nm, exhibits resonance Raman spectra. Overtone progressions of ν1(Re-Re) and ν2(Re-I), both A1g, and many combination tones are observed. The spectroscopic constants are calculated to be ω1 =258,5 cm -1 , x11 = - 0,42 cm-1 ; ω2 -153,0 cm-1 , x12 = - 0,32 cm-1.
Bindungsisomere Hexakis(thiocyanato-isothiocyanato)osmate(III) /Bond-Isomeric Hexakis(thiocyanato-isothiocyanato)osmates(III)
Authors: Preetz W. , Peters G.
Published: February 2015

On treatment of K2[OsX6], X = Cl, Br, I with KSCN in aqueous solution mixtures of bond-isomeric hexakis(thiocyanato-isothiocyanato)complexes, [Os(NCS)n(SCN)6-n] 3-, n = 1-6, are formed. At low temperatures and short reaction times species with more S-bonded, after longer boiling species with more N-bonded ligands are preferred, indicating the increase of thermodynamic stability with growing n-values. The isolation of the pure bond isomers n = 1-6, is achieved by ion exchange chromatography on diethylaminoethyl-cellulose. The assignment of the individual species is based upon the intensity ratios of characteristic group frequencies in the IR and Raman spectra. The UV-VIS spectra also show significant shifts within the series.
Reaktionen polyhalogenierter Cyclobutene mit Trimethylphosphit /Reactions of Polyhalogenated Cyclobutenes with Trimethylphosphite
Authors: Bauer Gert , Hagele Gerhard
Published: February 2015

Structure and reactive behaviour of polyhalogenated cyclobutenes towards trimethyl phosphite are studied in detail. Stable phosphoranes RP(F)(OCH3)3 as intermediates of Arbuzov-type reactions are obtained. Controlled decomposition of phosphoranes leads to highly reactive cyclobutenyl substituted phosphonic acid esters RP(O)(OCH3)2. Substitution reactions at aliphatic and vinylic positions of RP(O)(OCH3)2 are observed. Biphosphonic acid esters R[P(O)(OCH3)2]2 are synthesized. Some routes to perhalogenated cyclobutenes are described. NMR and MS data for the hitherto unknown cyclobutenyl-substituted organophosphorus compounds are given.
Na3FeS3, ein Thioferrat mit isolierten [Fe2S6]-Anionen /Na3FeS3, a Thioferrate with Isolated [Fe2S6]-Anions
Authors: Müller Paul , Bronger Welf
Published: February 2015

Na3FeS3 can be synthesized by the reaction of sodium carbonate with iron sponge at 1000 K under a stream of H2S. X-ray investigation on single crystals revealed its structure. The monoclinic unit cell contains four formula units, the space group is P21/n. The iron and sulphur atoms form isolated [Fe2Se6]-anions, consisting of two edge-sharing tetrahedra, with which the sodium atoms build up a three-dimensional arrangement.
Funktionelle Trimethylphosphinderivate, XIII Stabilisierte Carbanionen: Die Molekülstruktur von {[(CH3)3P]3C}I2/Functional Derivatives of Trimethylphosphine, XIII Stabilized Carbanions: The Molecular Structure of {[(CH3)3P]3C}I2
Authors: Zimmer-Gasser Beate , Neugebauer Dietmar , Schubert Ulrich , Karsch Hans H.
Published: February 2015

The title compound crystallizes in the space group Cmc21 with a = 1086(1), b = 1333(1) and c - 1264(1) (Z = 4). The cation exhibits Cs-symmetry with a crystallographic mirror plane perpendicular to the plane of the cation. Thus only two of the three phosphonium groups are stereochemically equivalent. In the planar P3C-moiety the P-C distances are 175 pm, the P-C-P angles 126.5° and 116.7°, respectively.
Metallacycloalkane, III Darstellung und Charakterisierung von a.a′-Dipyridyl-Nickelacyclopentan /Preparation and Characterisation of a,a′-Bipyridyl-nickelacyclopentane
Authors: Binger Paul , Doyle Michael J. , Krüger Carl , Tsay Yi-Hung
Published: February 2015

The title compound was synthesised from bis-1,5-cyclooctadienenickel, a,a′-bipyridyl and 1,4-dibromobutane in 83% yield and its structure determined by X-ray diffraction (a = 16.600, b = 10.837, c = 14.815 Å; β = 153.05°; C2/c, Z = 4; symmetry: C2 with square planar coordinated nickel; Ni-C: 1.949 Å).

a,a′-Bipyridylnickelcyclopentane reacts with maleic anhydride or methylacrylate under reductive elimination to give cyclobutane in 75 and 57% yield; considerable amounts of butenes are formed, in addition to cyclobutane, upon reaction with borontrifluoride-dibutylether or on thermolysis.
Dielectric Measurements and Molecular Structure. Styrene Oxides and Phenylcyclopropanes
Authors: Sorriso Salvatore
Published: February 2015

The effects of electronic structure and conformation of the molecules

(Y = o, m, and p-Cl) and

(Y′ = o, and m-Cl) have been studied in benzene between 10.0 and 70.0 °C. In the oxirane systems the conjugation between the two rings is very small, if present at all; consequently, in the absence of steric and/or electrostatic hindrance internal rotation is observed. In the cyclopropane systems examined these steric effects are sufficiently important to completely immobilise the molecular structure.
Die Synthese eines Cephamderivats mittels Vierkomponenten-Kondensation /The Synthesis of a Cepham Derivative by Four Component Condensation
Authors: Schutz Albrecht , Ugi Ivar , Kabbe Hans-Joachim
Published: February 2015

A five-step synthesis of a cepham derivative from a known, a,β,β-trihydroxyisobutyraldehyde derivative (1) and the sodium thioenolate of C-formyl N-phthaloyl methyl glycinate (2) is described. The key step of the synthesis is a four component condensation.
Notizen: Neue Thiaza-λ5. λ5 -diphosphetidine /New Thiaza-λ5,λ5-diphosphetidines
Authors: Zeiß Werner , Henjes Herbert , Lux Dieter , Schwarz Wolfgang , Hess Heinz
Published: February 2015

A new synthetic route to N-alkyl substituted thiaza- λ5, λ5-diphosphetidines 2a-c is given. NMR spectroscopy shows cis-trans isomerism for 2a and 2b. The crystal structure of trans-2c, the first example of a (P2NS)-four membered ring compound, was determined, exhibiting structural elements from 1 as well as from 3.
Notizen: Darstellung und Eigenschaften von trans-Diiodo-tetrakis(pyridin)osmium(II)/Preparation and Properties of /trans-Diiodo-tetrakis(pyridine)osmium (II)
Authors: Behrensdorf J. , Hasenpusch W. , Preetz W.
Published: February 2015

K2[OsI6] reacts with pyridine and glycerin to give dark red crystals of trans-[OsI2(py)4], soluble in organic solvents, insoluble in water, and sublimable in vacuum at 360 °C. The structure is established by vibrational and mass spectra. From solutions in non-polar solvents with gaseous HX (X = Cl, Br) adducts of type trans-[OsI2(py)4] ·2 HX are precipitated, which are soluble in water with blue colour.
Basic Chromium(III) Carboxylates: Reactions of Chromium(III) Chloride with Some Carboxylic Acids
Authors: Kapoor Ramesh
Published: February 2015

Anhydrous chromium(III) chloride reacts with pure carboxylic acids (RCOOH where R = CH3, C2H5, n-C3H7, CH2Cl, CHCl2 and CCl3) to give basic trinuclear chromium(III) carboxylates of the general formula [Cr3O(OOCR)6]+Cl-. The reaction of CrCl3 with acetic anhydride, however, gives a partially substituted product, CrCl(OOCCH3)2.The formation of basic carboxylates has been attributed to the strong affinity of Cr3+ ions for water that they can abstract it even from pure carboxylic acids. Their addition compounds with ammonia have also been prepared. The compounds have been characterized by their elemental analyses, IR, molar conductance and magnetic measurements.
Darstellung und Struktur der Verbindungen MgCuP, BaCuP(As) und BaAgP(As) / Preparation and Crystal Structure of MgCuP, BaCuP(As), and BaAgP(As)
Authors: Mewis Albrecht
Published: February 2015

The ABX-compounds MgCuP, BaCuP(As) and BaAgP(As) have been prepared and their structures determined. MgCuP crystallizes orthorhombically in an anti-PbCl2-structure (space group Pnma-D16
2h, a = 653.2(1) pm, b - 383.5(1) pm, c = 717.0(1) pm). The compounds BaCuP(As) and BaAgP(As) are isotypic and crystallize in a modified Ni2ln-structure (space group P63/mmc-D4
6h) with the lattice constants:

BaCuP a = 423.9(1) pm, c = 900.6(2) pm,

BaCuAs a = 437.2(1) pm, c = 907.3(2) pm,

BaAgP a = 449.6(1) pm, c = 882.8(2) pm,

BaAgAs a = 461.3(1 )pm, c = 889.6(1) pm.
Beiträge zur Untersuchung anorganischer nichtstöchiometrischer Verbindungen, IXa Elektronenmikroskopische Untersuchungen an Kristallen aus Transportexperimenten -System Nb2O5-WO3 (I) / Contributions to the Study of Inorganic Non-Stoichiometric Compounds, IXa Electron Microscopical Investigations on Crystals Prepared by Chemical Transport in the System Nb2O5-WO3 (I)
Authors: Heurung Günter
Published: February 2015

Compounds near the composition Nb2O5: WO3 ~ 6:1 were prepared by chemical transport (at relatively low temperatures). The block structures of the obtained samples were investigated by high resolution electron microscopy.

Besides unusual defects microdomains were found which still contain edgesharing blocks even at the composition 0/ΣMe = 2.53 to 2.55.
Synthesis of 3-(1-Methyl-5-nitro-2-benzimidazolyl)acrylic Acid Derivatives as Expected Antischistosomal Agents
Authors: Omar Nabil M. , Farag Hassan H. , Omar Farghaly A.
Published: February 2015

Several ester and amide derivatives of 3-(1-methyl-5-nitro-2-benzimidazolyl)acrylic acid have been prepared for testing as potential antischistosomal agents. The starting acid was conveniently synthesized from the corresponding aldehyde derivative through the Knövenagel-Döbner reaction. The utility of EEDQ as a coupler for the synthesis of peptides has been successfully extended to the coupling of N-heterocyclic acrylic acid derivatives and various amines.
Anwendung von 119Sn-FT-NMR bei Austauschreaktionen: [(CH3)2SnS]3 und [(CH3)2SnNC2H5]3 / Application of 119Sn-FT-NMR in Exchange Reactions: [(CH3)2SnS]3 and [(CH3)2SnNC2H5]3
Authors: Wrackmeyer Bernd
Published: February 2015

119Sn-NMR spectra of a 1:1 mixture of [(CH3)2SnS]3 (1) and [(CH3)2SnNC2H5]3 (2) were recorded to demonstrate the utility of 119Sn-FT-NMR in exchange reactions.
Intramolekularer Ringschluß und Umlagerung von Pyridinium-Salzen mit Carboxamidgruppe / Intramolecular Cyclisation and Rearrangement of Pyridinium Salts with Carboxamide Group
Authors: Gündel Wolf-H.
Published: February 2015

In früheren Publikationen hatten wir berichtet, daß quartäre Pyridinium-Salze Carboxamide unter
Kristallstruktur von Mangan(II)sulfit-Trihydrat, α-MnSO3·3H2O / Crystal Structure of Manganese(II)sulfite Trihydrate, α-MnSO3·3H2O
Authors: Engelen B. , Freiburg C.
Published: February 2015

The structure of α-MnSO3·3H2O, space group P21/n, Z = 4, Dm = 2.42, Dx = 2.425gcm-3, a = 6.6501(3), b = 8.9065(4), c = 8.7925(4) Å, β=96.105(3)°, was solved by the Patterson method and refined by Fourier and least-squares methods. All H atoms were located. The final R’s are 2.1/3.2% for the 1749 observed/2280 measured reflexions. Coordination of Mn is octahedral involving O atoms from three water molecules and three different sulfite groups. MnO6 octahedra are linked through sulfite sulfur. The Mn-O distances range from 2.149(2) to 2.314(2) Å. The S-O distances of the sulfite group are 1.529(2), 1.529(2) and 1.544(2) Å. The first two are elongated by one, the latter by two H bonds. The O-S-O angles are 103.25(9), 104.18(9) and 104.35(9)°.
Synthesis and Mesomorphic Properties of New Liquid Crystalline Cyclohexyl-phenyl- and Dicyclohexyl-pyrimidines
Authors: Villiger Alois , Boiler Arthur , Schadt Martin
Published: February 2015

Liquid Crystals, Cyclohexyl-phenyl-pyrimidines, Dicyclohexyl-pyrimidines The synthesis and mesomorphic properties of three new classes of cyano-substituted cyclohexyl-phenyl-and dicyclohexyl-pyrimidines are reported. The compounds are colourless, chemically and photochemically stable and have wide nematic mesophases. The thermal compatibility of the new compounds with other nematic liquid crystals is excellent. The large static positive dielectric anisotropics are shown to depend strongly on the position and number of hydrogenated rings as well as on the alkyl chain lengths within a homologous series. The reported bulk viscosities vary considerably among homologues. Hydrogenating the ring adjacent to the cyano end group causes η to increase, whereas a considerable viscosity reduction compared to nonhydrogenated homologues was found by hydrogenating the ring adjacent to the alkyl end group. The measured refractive indices of the new compounds are comparable to those of biphenyls.
Oberflächenverbindungen von Übergangsmetallen, XXII [1]. Die Umsetzung von Oberflächen-Chrom(II) auf Silicagel mit Olefinen bei höherer Temperatur. - Zum Mechanismus von Aufbau-, Abbau-, Metathese- und Isomerisierungs-Reaktionen an koordinativ ungesättigten Oberflächen-Metallionen / Surface Compounds of Transition Metal, XXII [1]. The Reaction of Surface Chromium(II) on Silica with Olefins at Higher Temperature. - A Contribution to the Mechanism of Growth, Degradation, Metathesis and Isomerization on Coordinatively Unsaturated Surface Metal Ions
Authors: Krauss Hans-Ludwig , Hums Erich
Published: February 2015

With chromium(II) supported on silica, at T > 150 °C olefins undergo growth/degradation/metathesis reactions by addition/elimination of even and uneven chain fragments including Ci. Simultaneously, catalytic double bond isomerization and C-rearrangements to methyl branched olefins occur. One mechanism is proposed for all these reactions via a pseudo-tetrahedral MC3 intermediate. Polyethylene synthesis at lower temperatures may follow the same way. For growth/degradation/metathesis the formation of a metal carbene unit is postulated as a characteristic, step; in case of ethylene, >Cr=CH2 will be formed as a precursor of the final CH4 (resulting from a secondary reaction with support hydrogen).
Die Monoantimonide RbSb und CsSb / The Monoantimonides RbSb and CsSb
Authors: Georg von Schnering Hans , Hönle Wolfgang , Rrogull Gabriele
Published: February 2015

The alkali metal monoantimonides RbSb and CsSb were synthesized from the elements in sealed quartz ampoules. These compounds crystallize in the NaP-type structure (RbSb: P212121 (No. 19), a = 731.5pm, b = 719.7 pm, c = 1281.5 pm, Z = 8; CsSb: P212121 (No. 19), a = 757.6 pm, b = 734.5 pm, c = 1327.3 pm, Z = 8). The main feature of the structures are 1
∞[Sb-] chains parallel to the 5-axis with bond distances. d̄(Sb-Sb) = 285.8 pm and 285.3 pm, respectively. These bond lengths are discussed in detail relative to those in elementary antimony and to the tetrahedral or covalent radii. The volume increment of Sb- can be derived to be 29.8 cm3 · mole-1.
Die Kristallstruktur des Rubidiumtrimolybdatosulfats Rb2SMo3O13 / The Structure of the Rubidiumtrimolybdatosulfate Rb2SMo3O13
Authors: Fuchs Joachim , Kreusler Hans-Ulrich , Förster Achim
Published: February 2015

By acidification of an aqueous solution of Rb2MoO4 with sulfuric acid the rubidium trimolybdatosulfate Rb2SMo3O13 · 0.72 H2O is formed. A compound with the same composition and evidently the same structure but free of crystal water is obtainable by melting a mixture of Rb2SO4 and MoO3 in molar ratios 1:3. The X-ray structure investigation shows the anion to be built up from double chains of MoO6 octahedra. Always three neighbouring octahedra are linked about common vertices with one SO4 tetrahedron. The tetrahedra are alternating above and below the double chain. - Rb2SMo3O13 is the first known macromolecular heteropolymolybdate.
Nitrogen-14 Nuclear Quadrupole Resonance in Some Hexanitro Complexes of the Type R2PbCu(NO2)6
Authors: Asaji Tetsuo , Ikeda Ryuichi , Nakamura Daiyu
Published: February 2015

The nuclear quadrupole resonance of nitrogen-14 was observed for potassium, ammo­nium, rubidium, and thallium lead hexanitrocuprates(II) at various temperatures below the second highest transition temperature of each complex. All the compounds except the ammonium salt yielded two practically same sets of the quadrupole parameters, eQq/h and η, indicating the presence of at least two crystallographically different but very similar kinds of nitrogen atoms in the crystals. For the ammonium salt, three phase transitions at 94.5, 287, and 316 K were located from the experiments of DTA and NQR. The crystals of the highest and the second highest temperature phases were proved to be i8omorphous with those of the remaining complexes in their highest and intermediate temperature phases, respectively. The salt yielded two sets of the quadrupole parameters between 287 and 94.5 K, and only one sot below 94.5 K down to 4.2 K, indicating that a structural phase transition takes place at 94.5 K. No resonance could be observed in the highest and the second highest temperature phases of all the complexes studied. The covalency of copper-nitrogen bonds in lead hexanitrocuprates(II) is estimated at about 10% from the quadrupole parameters observed at 4.2 K. The structure of the complex anion is discussed in relation to the Jahn-Toller distortion.
Der retentive Verlauf nukleophiler Substitutionen an 7-exo-Norcaryltriflat [1] / Retentive Reaction of Nucleophilic Substitutions with 7-exo-Norcaryltriflat [1]
Authors: Dauner Harald , Lenoir Dieter , Ugi Ivar
Published: February 2015

The SN reactions of 7-exo-norcaryl triflate with strong nucleophiles (Clθ, Brθ, N3
θ) under SN2 conditions proceed with complete configurational retention. The 30-50% by­products are non-isomeric and are presumably formed by elimination and subsequent oligomerization.
Reaktionen von SbCl5 mit Acetoaeetanilid / Reactions of SbCl5 with Acetoacetanilide
Authors: Dietrich W. , Eisinger H. K. , Latscha H. P.
Published: February 2015

Antimony(V) Chloride, Acetoacetanilide At room temperature acetoacetanilide and antimony(V) chloride form a 1:1-(1) and a 1:2-adduct (2). These adducts react to the heterocycles C10H10Cl4NO2Sb (3) and C10H9Cl5NO2Sb (4). 3 exists in solution in two stereoisomers. The Free Energy of Activation for the transformation of the isomers is estimated.
Zur Reaktion von Trimethylsilyl-difluorophosphat, Trimethylsilyl-dimethylphosphinat und Difluorophosphorsäureanhydrid mit TiCl4 bzw. SbCl5 / On the Reactions of Trimethylsilyl Difluorophosphate, Trimethylsilyl Dimethylphosphinate and Difluorophosphoric Acid Anhydride with TiCl4 and SbCl5, respectively
Authors: Shihada Abdel-Fattah , Mohammed Abdulalah T.
Published: February 2015

TiCl4 reacts with trimethylsilyl difluorophosphate (Me3SiPO2F2) and with trimethylsilyl dimethylphosphinate (Me3SiPO2Me2) at room temperature under cleavage of the Si-O bond to give the principal products Cl2Ti(PO2F2)2 and Cl2Ti(PO2Me2)2, respectively. The former product has also been obtained from the reaction of P2O3F4 with TiCl4-SbCl5 is capable of cleaving the P-O bond in P2O3F4 to give Cl4SbPO2F2, but forms addition compounds with Me3SiPO2F2 and Me3SiPO2Me2 in which the terminal oxygen atoms of the esters are bound to antimony. IR spectra have been used to elucidate the structures of the prepared compounds.
Chemie polyfunktioneller Liganden, 56 [1]. Darstellung von N-Deutero-bis(diphenylphosphino)amin, sowie schwingungsspektroskopischer Vergleich mit Bis(diphenylphosphino)amin und Lithium-bis(diphenylphosphino)amid / Chemistry of Polyfunctional Ligands, 56 [1]. Preparation of N-Deutero-bis(diphenylphosphino)amine, as well as the Vibrational Spectroscopic Comparison with Bis(diphenylphosphino)amine and Lithium-bis(diphenylphosphino)amid
Authors: Eilermann Jochen , Lietz Martin
Published: February 2015

Bis(diphenylphosphino)amine, [(C6H5)P2NH (1), can be metallated with n-butyl-lithium to hthium-bis(diphenylphosphino)amid, [(C6H5)P2NLi (2), It reacts with CH3OD to give N-Deutero-bis(diphenylphosphino)amine, [(C6H5)P2ND (3). The compounds were characterized by infrared, Raman, 1H and 31P NMR spectroscopy.
Reaktionen von Dicarbonyl (η-cyclopentadienyl)(propiolsäuremethylester)niangan(I) mit Basen. Isolierung von Vinyliden- und Carbenkomplexen / Reactions of Dicarbonyl(η-cyclopentadienyl)(methylpropiolate)manganese(I) with Bases The Isolation of Vinylidene and Carbene Complexes
Authors: Berke Heinz
Published: February 2015

Reaction of dicarbonyl(η-cyclopentadienyl)(methylpropiolate)manganese(I) with various stoichiometric quantities of tert-butyl lithium and subsequent addition of HCl or CH3OSO2F allows the isolation of vinylidene complexes of the general type CpMn(CO)2=C=CR1R2 R1=H, CH3; R2 = COOCH3, COt-Bu, COH(t-Bu)2). The compound with R1=H, R2=COOCH3 adds another CpMn(CO)2 fragment, with formation of a bridged vinylidene species with a Cp2Mn2(CO)4 unit. The reaction with amide or methoxide leads to the formation of carbene complexes CpMn(CO)2 = C(R1)CH2-COOCH3 (Rx = NH2, OCH3).
Beiträge zur Chemie des Bors, CVIII [1]. Synthese und Konformation yon N.N'-Bis(boryl)-N.N'-dimethylhydrazinen / Contributions to the Chemistry of Boron, CVIII [1]. Synthesis and Conformation of N,N , -Bis(boryl)-N,N'-dimethylhydrazines
Authors: Barlos K. , Nöth Heinrich
Published: February 2015

A series of bis(boryl)hydrazines X(CH3)B-CH3N-NCH3-B(CH3)X (X = F, Cl, Br, SCH3, N(CH3)2, CH3) has been prepared by various methods and investigated by NMR, MS and PE Spectroscopy. The new oxidative ring opening of 2, 3, 4, 5-tetramethyl-1-thia- 3,4-diaza-2,5-diborolidine by bromine to yield Br(CH3)B-CH3N-NCH3-B(CH3)Br and sulfur yields the syn/syn conformer which rapidly adopts also the syn/anti and the thermodynamically favoured anti/anti conformation. All bis(boryl)hydrazines possess planar geometry at the nitrogen atom as suggested by the 14N NMR data and adopt gauche conformation as indicated by their He(I)-photoelectron spectra.
BaSbTe3 und BaBiSe3 Verbindungen mit BiSe-bzw. SbTe-Schichtverbänden / BaSbTe3 and BaBiSe3 Compounds with BiSe-or SbTe-Layer Structures, Respectively
Authors: Volk Klaus , Cordier Gerhard , Cook Ralph , Schäfer Herbert
Published: February 2015

The new compounds BaBiSe3 and BaSbTe3 crystallize in the orthorhombic system, space group P212121 with

BaBiSe3: a = 1724 ± 2 pm, b = 1600 ± 2 pm, c = 437.0 ± 0.5 pm;

BaSbTe3: a = 1809 ± 2 pm, b = 1694 ± 2 pm, c = 463.5 ± 0.4 pm.

BiSe6
- or SbTe6
- octahedra, resp., are connected by common edges to fourfold strings. These are bound by additional chalcogen atoms to sheets, between which the Ba ions are located.
Metallkomplexe der Phosphinsäuren, XVI [1]. cis-trans-Isomerie bei planaren Palladiumund Platinkomplexen [RR′ PS2]2M [2] / Metal Complexes of Phosphinic Acids, XVI [1]. cis-trans Isomers of Planar Palladium and Platinum Complexes [RR'PS2]2M [2]
Authors: Kuchen Wilhelm , Uppenkamp Reinhard
Published: February 2015

Unsymmetrically substituted dithiophosphinic acids RR'P(S)SH give planar metal chelates [RR'PS2]2M 1 [M = Pd(II), Pt(II)]. It can be shown by comparison of their 31P-{1H} NMR spectra with those of symmetrically substituted compounds [R2PS2]2M that in the synthesis of 1 equimolar mixtures of the cis and trans isomers are formed.
Die Struktur des Rubidiumtrimolybdathydrats Rb2Mo3O10 · H2O / The Structure of the Rubidiumtrimolybdate Hydrate Rb2Mo3O10 · H2O
Authors: Kreusler Hans-Ulrich , Förster Achim , Fuchs Joachim
Published: February 2015

For the first time single crystals of trimolybdate were obtained through a slow trans-formation of the primary precipitate in a slightly acidified solution of rubidium molybdate at a temperature of 70 °C.

A structural analysis of Rb2Mo3O10 · H2O revealed that the anion forms a chain with a hexameric identity period built up from MoO6 octahedra. Each Mo atom is bonded with two terminal oxygen atoms. The anion doesn't contain OH groups.
ESR of a Cyclic Phosphahydrazidinyl
Authors: Neugebauer Franz A. , Fischer Hans
Published: February 2015

The cyclic phosphahydrazidinyl (5) was gen-erated and studied by ESR. The results are discussed in connection with the properties of other hydrazidinyl radicals.
MO4O8((CH3)2POS)4, ein Molybdän(V)-Sauerstoff-Kuban / MO4O8((CH3)2POS)4; a Molybdenum(V) Oxygen Cubane
Authors: Mattes Rainer , Mühlsiepen Karl
Published: February 2015

The tetranuclear complex Mo4O8((CH3)2POS)4 has been synthetized by reacting MOCl5 with Na((CH3)2POS) in CHCl3/CCl4 solutions. The structures of two crystalline modifications (I and II), containing different amounts of solvent, have been determined by X-ray crystallography. In both, four molybdenum and four oxygen atoms are situated at the corners of a highly distorted cube. Each Mo atom has a terminal oxo group. The Mo atoms form two MO2 pairs through Mo-Mo bonds. The bidentate (CH3)POS- ligands coordinate to two Mo atoms of different pairs. The sulfur atoms of the ligands are partially replaced by oxygen atoms.
Massenspektrometrische Untersuchungen an Borchelaten, V [1] Fragmentierung borhaltiger aromatischer Azoverbindungen / Mass Spectrometric Investigation of Boron Chelates, V [1]Fragmentation of Aromatic Azo Compounds Containing Boron
Authors: Hohaus Eberhard , Riepe Wolfgang , Wessendorf Klaus
Published: February 2015

Differing fragmentation of boron chelates of aromatic azo compounds confirms the structural formulae 1a-7c, presented in [2].

More significant differences are caused by the substituent of the boron R (F instead of C6H5).

Although certain rules can be deduced by the substitution of F for CeHs with regard to the change in intensity of the ions M+, M+-R (and others), in some cases the stable aromatic azo system causes a significant change in the fragmentation as compared with that of azomethine chelates. The chelates 7 eliminate “RH” and show no molecular ion. Apparently a second chelate ring is closed before further fragmentation can start. Fragmentation of 7 a and b is analogous to 5.
AsPh4)2[Re2FN2Cl7], ein μ-Fluoro-Nitridokomplex des Rhenium(VI) / (AsPh4)2[Re2FN2Cl7],a μ-Fluoro Nitrido Complex of Rhenium(VI)
Authors: Liese Werner , Dehnicke Kurt , Pebler Jürgen
Published: February 2015

(AsPh4)2[Re2FN2Cl7] is prepared by the reaction of ReNCL4 with AsPh4F in acetonitrile solution. The IR spectrum indicates a bridging Re-F-Re complex anion with terminal Re ≡ N ligands. The magnetic susceptibility was measured in the temperature range of 4.8-280 K. The effective magnetic moment is 1.66 B.M. per Re atom (θ = -0.5 K) and corresponds well with Re(VI). The magnetic moment of the well known PPh4[ReNCl4] has also been studied {μeff = 1.67 B.M.; θ = -1.2 K).
Oxotitanate mit gemischter Valenz, III Zur Kenntnis von BaTi8O16 / Oxotitanates with Mixed Valence, III About BaTi8O16
Authors: Schmachtel J. , Buschbaum Hk. Müller-
Published: February 2015

The hitherto unknown compound BaTi8O16 was prepared by heating a mixture of BaO:TiO2 = 1:4 in a vacuum furnace to 1400 °C (Ti crucible).

Single crystal X-ray investigations show monoclinic symmetry (a = 1420,9, b = 297,1, c = 998,1 pm, β = 133,50°; space group C2
3-C2). The crystal structure was found to be isotypic to α-MnO2.
Tricarbonyl(η4-1.5-cümethylen-2.6-cümethylcyclooctan)eisen: photochemische Synthese und Struktur / Tricarbonyl(η4-1,5-dimethylene-2,6-dimethylcyclooctane)iron: Photochemical Synthesis and Structure
Authors: Grevels Friedrich-Wilhelm , Schneider Konrad , Krüger Carl , Goddard Richard
Published: February 2015

Extended photolysis of pentacarbonyliron in neat 2,3-dimethylbutadiene results in dimerization of the diene and formation of tricarbonyl(η4-1,5-dimethylene-2,6-dimethylcyclooctane) iron (1). The structure of complex 1 is characterized by a trigonal-bipyramidal geometry whereby the exocyclic double bonds of the diene ligand and one of the carbonyl groups lie exactly in the equatorial coordination plane.
Synthese und herbizide Wirksamkeit der D- und L-Enantiomeren des 2- [4-(2.4-Dichlorphenoxy)-phenoxy] -propionsäure-methylesters / Synthesis and Herbicidal Activity of the D- and L-Methyl 2-[4-(2,4-Dichlorophenoxy)-phenoxy]-propionate Enantiomers
Authors: Jürgen Hans , Bieringer Hermann
Published: February 2015

The D- and L-enantiomers of the wild oat herbicide diclofop-methyl (title compound) were prepared utilizing resolution operations and by synthetic routes with optically active compounds as starting material. The dextro-rotatory product which the D(R)-configuration can be attributed to, was found to be the herbicidally active species.