bluuebunny/crossref_metadata_2025 huggingface dataset:
Säure-Base-Eigenschaften des zyklischen Triamins N,N′,N″-Trimethyl-1,4,7-triazacyclononan: Die Kristallstruktur seiner monoprotonierten Form [C9H22N3]ClO4) / Acid-Base Properties of the Cyclic Triamine N,N′,N″-Trimethyl-1,4,7-triazacyclononane and Crystal Structure of its Monoprotonated Form [C9H22N3](ClO4)
Authors: Wieghardt K. , Brodka S. , Peters K. , Peters E. M. , Simon A.
Published: March 2015

The crystal structure of the monohydroperchlorate of N,N',N"-trimethyl-1,4,7-triazacyclo-nonane, [C9H22N3](ClO4), has been determined by single crystal X-ray diffraction. The acidic proton of the cation is bonded to one amine nitrogen and it forms hydrogen bonds to the other two N-atoms in agreement with a proposed model, which has been invoked to interpret successive protonation constants of cyclic triamines. The salt [Me6[9]aneN3](BF4)3 has also been prepared
Übergangsmetall-Komplexe mit Schwefelliganden, XXVII Synthese und Reaktivität der Nitrosyl-und Nitrido-Ruthenium-Komplexe mit 1,2-Benzoldithiolat-Liganden [Ru(NO)(S2C6H4) 2]- bzw. [Ru(N)(S2C6H4)2]- / Transition Metal Complexes with Sulfur Ligands, XXVII Synthesis and Reactivity of the Nitrosyl- and Nitrido-Ruthenium Complexes with 1,2-Benzenedithiolate Ligands [Ru(NO)(S2C6H4)2]- and [Ru(N)(S2C6H4)2]-, Respectively
Authors: Sellmann Dieter , Binker Gerhard
Published: March 2015

The reaction of [Ru(NO)2(PPh3)2], [RuCl(NO)2(PPh3)2]PF6 or [RuCl3(NO)(PPh3)2] with 1,2- benzenedithiolate(-2), C6H4S2
2-, leads to the 16e--complex [Ru(NO)(S2C6H4)2]-, which was isolated as the NBu4
+ salt (1). The square pyramidal anion in [NBu4)[Ru(NO)(S2C6H4)2] coordinates PMe3 with rearrangement of the sulfur ligands to give the six-coordinate cis- [NBu4][Ru(NO)(PMe3)(S2ChH4)2] (3); the rearrangement of the C6H4S2
2--Iigands from trans to cis coordination is proved by 13C NMR spectroscopy. [Ru(NO)(S2C6H4)2]- is rapidly reduced even under mild conditions. Reaction of 1 with NaBH4 in MeOH leads to the reduction of NO to a nitrido ligand and the concomitant oxidation of (formal) Ru(III) to Ru(VI) yielding [NBu4][Ru(N)(S2C6H4)2] (2). This compound is also formed when the nitrosyl complex is reacted withSiMe3N3.[Ru(NO)2(PPh3)2] and [RuCl(NO)2(PPh3)2]PFare denitrosylated by dttd2- (dttd2- = 2,3,8,9-dibenzo-1,4,7,10-tetrathiadecane(-2)) to give [Ru(dttd)(PPh3)2]
EPR and ENDOR of Sodium Complexes of Spin Labeled Monoazacrown Ethers
Authors: Sosnovsky George , Lukszo Jan , Gutierrez Peter L. , Scheffler Klaus
Published: March 2015

Sodium complexes 3 and 5 of the spin labeled monoazacrown ethers 2,2,15,15-tetramethyl-1-aza- 4,7,10,13-tetraoxacyclopentadecane-1-oxyl (2) and 1,4,7,10-tetraoxa-13-(2′,2′,6′,6′-tetramethyl-piperidine-1′-oxyl-4′-yl)azacyclopentadecane (4) were synthesized and studied by EPR and ENDOR spectroscopies. The hyperfine splitting parameter and the g value of the complex 5, containing the exocyclic nitroxyl moiety, were identical to the parent complexon 4, i.e., aN = 15.6 G. g = 2.0060 ± 0.0001. In contrast, the data for the complex 3, containing the endocyclic nitroxyl moiety were different. Thus, the spectrum of the complex 3 was a triplet of quartets with aN = 15.7 G. aNa = 2.47 G, g = 2.0062 ± 0.0001, whereas the spectrum of the parent complexon 2 was a triplet with aN = 15.5 G, g = 2.0059 ± 0.0001.

The interaction between the sodium cation and the nitroxyl moiety in 3 was further confirmed by the sodium ENDOR transition at 7.27 MHz
Synthese und Kristallstruktur von [N(PPh3)2][VCl3(N3S2)]·C7H8 / Synthesis and Crystal Structure of [N(PPh3)2][VCl3(N3S2)]·C7H8
Authors: El-Kholi Aida , Christophersen Ruth , Müller Ulrich , Dehnicke Kurt
Published: March 2015

[N(PPh3)2][VCl3(N3S2)]·C7H8 is formed by the reaction of VCl2 (N3S2) with excess PPh3 in CH2C12 and subsequent treatment of the reaction mixture with toluene, as well as by the reaction of VCl2(N3S2) with [N(PPh3)2]Cl in CH2Cl2 in the presence of toluene. The compound forms red crystals, which have been characterized by IR spectroscopy. The crystal structure was determined by X-ray diffraction (1433 observed, independent reflexions, R = 0.070). Crystal data: mono-clinic, space group Cc, Z = 4, a = 994.1, b = 2148.0, c = 2055.2 pm, β = 90.03°. The compound consists of [N(PPh3)2]⊕ cations and [VCl3(N3S2)]⊖ anions, in which the vanadium atom is five-coordinated by threee chlorine atoms and two nitrogen atoms, and is part of a planar VN3S2 ring.
Preparation and Pyrolysis of Stereoisomeric Bromobicyclo[n.1.0]alkanes ( n = 6, 8 , 10)
Authors: Dehmlow Eckehard V. , Kramer Roland
Published: March 2015

The title compounds la-3c were prepared by stereoselective reduction of the respective dibromides. Pyrolysis gave allylic bromides (8, 9, 11) as primary and dienes (10, 12) as secondary products. Product ratios were independent of the stereochemistry of the starting materials. No differences of the rearrangement rates of the stereoisomers were observed in gas phase reactions of the derivatives of bicyclo[6.1.0]- and bicyclo[8.1.0]alkanes. With the larger bicyclo[10.1.0] derivatives, however, distinct differences in the thermal stability of cis-trans-isomers4c/5c or 2c/3c were found in condensed phase.
Ternäre Varianten des Pyrit-Typs: Darstellung und Struktur von SrPt4P6, SrPt4As6, BaPt4As6 und BaPt2P3 / Ternary Pyrite-Type Derivatives: Preparation and Crystal Structure of SrPt4P6, SrPt4As6, BaPt4As6 and BaPt2P3
Authors: Wenski Guido , Mewis Albrecht
Published: March 2015

The isotypic compounds SrPt4P6 , SrPt4As6 and BaPt4As6 were found to crystallize with a Pyrite-type derivative structure (monoclinic, C2/c, Z = 4) in which one Sr or Ba atom per formula unit occupies the position of a P2 or As2 pair. BaPt2P3 forms another Pyrite-type related structure (monoclinic, P21/c, Z = 4) built up by Ba2Pt and Pt3P6 layers. All crystal structures were refined from four-circle diffractometer data, the lattice constants are:

SrPt4P6: a = 825.2(1) pm, b = 798.4(1) pm, c = 1142.8(1) pm, β = 90.74(2)°;

SrPt4As6: a = 858.2(1) pm, b = 832.1(1) pm, c = 1194.5(1) pm, β = 91.00(2)°;

BaPt4As6: a = 868.8(1) pm, b = 833.3(1) pm, c = 1197.1(1) pm, β = 90.81(2)°;

BaPt2P3 a = 835.2(1) pm, b = 577.6(1) pm, c = 1157.4(1) pm, β = 106.73(2)°.
Synthese und Struktur von H2NSO2NWCl4 - ein Kirsanov-Reagens mit einem Übergangsmetallatom / Synthesis and Structure of H2NSO2NWCl4 - a Kirsanov Reagent with a Transition Metal Atom
Authors: Witt Michael , Roesky Herbert W. , Noltemeyer Mathias , Sheldrick George M.
Published: March 2015

H2N-SO2 -NWCl4 (1) has been synthesized from WCl6 and SO2(NH2)2 , and forms adducts with donor solvents such as pyridine and acetonitrile. 1·CH3CN crystallizes in the space group P21/n with cell constants a = 652.5(1); b = 2325.3(2); c = 775.8(1) pm; β = 90.32(1)°. The nitrogen-tungsten bond length of 173.0 pm and the S-N-W bond angle of 169.3° indicate a W=N double bond.
Hydroxy Complexes of Gold 2. Calcium Aurates [1]
Authors: Jones Peter G. , Schelbach Ralf , Schwarzmann Einhard
Published: March 2015

Two calcium aurate phases have been obtained as single crystals, phase 1 from H AUC1 4 + Ca(OH) 2 and phase 2 from NaAu(OH) 4 + Ca(C10 4) 2 . An X-ray structure determination of 1 shows its composition to be Ca 2 (0H) 3 (H 2 0) 4 [Au(0H) 4 ]. The apparent space group is Cmcm, but this corresponds to a sub-cell of the true structure. The disordered Cmcm structure was refined to R 0.032 for 813 reflections. The coordination geometry is square planar at gold (Au-O 1.97, 1.99 Ä), cubic at Ca(l) and octahedral at Ca(2). Phase 2 crystallizes in a primitive tetragonal cell with a 6.94, c 7.71 Ä; it is probably Ca[Au(OH) 4 ] 2 , but this has not yet been confirmed by a full structure determination.
Ein neuer Weg zur Darstellung der Nitrosylkomplexe CpM(CO)2NO (M = Cr/Mo/(W)) durch NO/CO-Austausch zwischen [Co(NO)2Hal]2 und Carbonyl-cyclopentadienylkomplexen* / A Novel Route to the Nitrosyl Complexes CpM(CO)2NO (M = Cr/Mo/(W)) by NO/CO Exchange between [Co(NO)2Hal]2 and Carbonyl-cyclopentadienyl Complexes*
Authors: Brauel Anke , Rehder Dieter
Published: March 2015

The title compounds have been prepared by NO transfer from [Co(NO)2Hal]2 (Hal = Cl, Br, I) to [CpM(CO)3]2, CpM(H)(CO)3 and [CpM(CO)3]- (M = Cr, Mo, W; Cp = η5-C5H5). In the case of the neutral complexes, the reactions need initiation and support by light; the anionic complexes are nitrosylated in a dark reaction. The highest yields (60%) are obtained from the reactions between [Co(NO)2Br]2 and [CpM(CO)3]2 (M = Cr, Mo).
Neuartige discotisch-flüssigkristalline, polare Monothioscyllitol-Derivate [1,2] / Novel Discotic Liquid Crystalline, Polar Monothioscyllitol Derivatives [1,2]
Authors: Kohne Bernd , Marquardt Peer , Praefcke Klaus , Psaras Panicos , Stephan Werner
Published: March 2015

3-5

On the basis of an improved synthesis of the 1,3,4,5,6-pentaacetate of myo-inositol, now available in only one step from that cyclitol in yields up to 90%, we prepared various derivatives of 1-deoxy-1-mercapto-scyllo-inositol (monothioscyllitol) via the mesylate 1 a or the trifluoromesylate 1 b , respectively. The non-centrosymmtric disc-shaped thioethers 3a-h as well as their S,S-dioxides 4a-h and the S-oxide 5f exhibit thermotropic discotic mesophases over wide temperature ranges. The thermomesomorphism of these new sulfur compounds has been studied by optical microscopy and by differential scanning calorimetry. The pentabutyrates 3a and 4a as well as the dimesomorphic pentapentanoate 3 b exhibit a probably new type of discophase Dx whereas all other monothioscyllitol derivatives with longer alkyl chains show the Dho-phase over wide temperature ranges. Of some selected new thioethers 3, sulfones 4, and of the sulfoxide 5f the dipole moments have been measured which are highest with the cyano derivatives 3g and 4g at about 5 or above 6 D, respectively. These values characterize them as the strongest polar discogens studied so far.

The presented monothioscyllitol derivatives 3, 4 and 5 do not only increase the number of rarely known polar discogens, but also show that non-centrosymmetric and polar discotic liquid crystals with a small, alimonocyclic, saturated "core" now can be prepared easily. Their permanent electric dipole moments could give rise to interesting magnetic or electric field effects.
Amphiphilic Carbohydrate-Based Mesogens, 2 [1] Aldose Di-n-alkyl Dithioacetals: Novel Double-Tailed Thermotropic Liquid Crystals
Authors: Dahlhoff Wilhelm Volker
Published: March 2015

Mercaptolyses of the pentoses [D-lyxose (1), D-xylose (2), L-arabinose (3)] and hexoses [D-mannose (4), D-glucose (5), D-galactose (6)] with n-alkyl thiols having chain lengths ≥ C6 gives mesogenic aldose di-n-alkyl dithioacetals 7-12.
Synthese und Struktur von Phenyltetra(acetato)stiboran
Authors: Wieber Markus , Fetzer-Kremling Isa , Reith Hildegard , Burschka Christian
Published: March 2015

Phenyltetra(acetato)stiborane is obtained by reacting phenyldichlorostibane successively with sulfuryl chloride and silver acetate at low temperatures ( - 70 °C). An X-ray analysis of C6H5Sb[OC(O)CH3]4 shows, that the central antimony atom is hexacoordinated by chelation of one nearly symmetrically bonded acetate group, a phenyl group, and three singly-bonded acetate ligands.
Charge Transfer in MX3 • CH3CN (M = Al, Ga; X = Br, I) by Means of 14N, 27Al, 69Ga, 81Br, and 127I NQR
Authors: Okuda Tsutomu , Yamada Koji , Ishihara Hideta , Ichiba Sumio
Published: March 2015

NQR spectra were observed in the 1:1 complexes of CH3CN with AlBr3, AlI3, and GaBr3. The NQR data suggest that these complexes consist of the molecular species MX3 · CH3CN. The electron populations on the resonant nuclei and the charge transfer between N and metal atoms were estimated according to the Townes-Dailey treatment. The results show that the amount of the charge transfer in these complexes is large.
Metallorganische Reaktionen konjugierter Azomethine, IV [1] Katalytische Synthese substituierter Cyclohexane aus Butadien und 1-Azadienen an π-Allyl-Palladium-Komplexen
Authors: Dieck Heindirk tom , Müller Christiane , Haupt Erhard T.K. , Bolze-Kuhrt Dörte
Published: March 2015

The reaction of dimeric π-allyl palladium chloride with 1-azadienes 1 ( R -N = CH-CH = CH-R') affords the mononuclear complexes (π-Allyl)Pd(L)Cl 2. Two independent intramolecular rotational motions are detected by NMR methods. These complexes (with R ' = Aryl) react with silver tetrafluoroborate, preferentially in the presence of 1, to the cationic complexes [(π-Allyl)Pd(L)2]+ BF4
-, 3, which are also non-rigid with respect to ligand rotation on the NMR time scale. Complexes 3 catalyse the 2 :1-cyclo-cooligomerization of butadiene and 1-azadienes. This reaction to compounds 4 constitutes the first example of a very regio- and stereoselective formation of cyclohexanes from three C = C double bonds. The structure, substitution pattern and conformation of 4 are assigned on the basis of 2D -correlation NMR spectroscopy.
Phosphinsubstituierte Chelatliganden, XXV [1] Diastereoselektive Komplexierung chiraler Phosphinothioformamide mit entferntem Asymmetriezentrum
Authors: Kunze Udo , Burghardt Roland
Published: March 2015

For further studies of the diastereoselective complex formation of ambidentate chiral chelating ligands, we prepared the racemic phosphinothioformamides. Ph2P(X )C(S)NHC*HR 1R2, with X = 2e- (R1 = Ph,R2 = Et: 1a;R1 = Ph,R2 = iPr:2a; R2 = Me,R2 = Et:3a) and X = O (1b ,2b ) according to a previously reported route. The coordination of 1a -3a to CpM (CO)3Cl (M = Mo, W) in m ethanol gives the diastereomeric P.S-chelate complexes,

(Mo: 4-6, W: 7-9). In solution, epimerisation proceeds to an equilibrium ratio of B/A = 1,5 in case of 4, 5, 7, and 8, but less than 1,1 with 6 and 9. A reduced diastereoselectivity (d.e. 10 -20%) is also observed during the formation of the analogous molybdenum complexes 10a-d with phosphine ligands derived from α-amino acid esters. Ph2PC(S)NHC*H(R)COOMe [R = Me (L-Ala), CH2Ph (L-Phe). CHMe2 (L-Val). Ph (D-phenylglycine)]. The results indicate a significant asymmetric induction despite of the four bond distance of the chiral centres.
Photochemistry of Pesticides, 10 [1] Photodegradation of O,O-Diethyl-S(3,4-dihydro-4-oxobenzo[d][1,2,3]triazin- 3-yl-methyl)phosphorodithioate (Azinphos-ethyl)
Authors: Abdou W. M. , Sidky M. M. , Wamhoff H.
Published: March 2015

The photodegradation of Azinphos-ethyl (1) in chloroform and methanol solution has been studied. 3,4-Dihydro-3-methyl-4-oxobenzo[d][1,2,3]triazine (3), 3,4-dihydro-4-oxo-benzo[d]- [1,2,3]triazine (5), O,O-diethyl-O(3-methylbenzo[d][1,2,3]triazine-4-yl)p hosph ate (8), N-methylanthranilic acid (11) (in methanol: methyl ester 12), and sulfur have been isolated and characterized as photoproducts. The decay mechanism is discussed.
Zur Reaktion von (η5-C5H5)Fe(CO)2Br mit Se(SiMe3)2 Die Kristallstruktur von [Se{Fe(CO)2(C5H5)}3]2[Fe4Se4Br4]
Authors: Fenske Dieter , Maué Paul , Merzweiler Kurt
Published: March 2015

(η5-C5H5)Fe(CO)2Br reacts with Se(SiMe3)2 to form the title compound 1, which has been characterized by X-ray crystal structural analysis. 1 crystallizes in the space group P212121 with 4 formula units per unit cell. 1 consists of [Se{Fe(CO)2(C5H 5)}3]+- cations and [Fe4Se4Br4]2--anions, the latter with a heterocubane structure.
Synthese und Kristallstruktur des Phosphaniminatokomplexes [MoCl4(NPPh3)(Pyridin)] · CH2Cl2/ Synthesis and Crystal Structure of the Phosphaneiminato Complex [MoCl4(NPPh3)(pyridine)] · CH2Cl2
Authors: Völp Karin , Weller Frank , Dehnicke Kurt
Published: March 2015

[MoCl4(NPPh3)(pyridine)] · CH2Cl2 is formed by the reaction of the cyclothiazeno complex [MoCl3(N3S2) · (pyridine)] with triphenylphosphane in CH2Cl2 solution. It forms red, moisture sensitive needles. [MoCl4(NPPh3)(C5H5N)] · CH2Cl2 crystallizes monoclinically in the space group P21/n with four formula units per unit cell (1934 independent observed reflexions. R = 0.057). The cell dimensions are a = 1165, b = 1473, c = 1696 pm; β = 107.82°. The Mo atom is coordinated by four chlorine atoms, by the N atom of the (NPPh3
-) ligand, and in trans-position to it by the N atom of the pyridine molecule. The Mo= N = PPh3 group has a nearly linear MoNP axis (176.6°) with bond lengths of MoN = 172 pm and PN = 165 pm.
Phosphinocyclopentadienid via Cyclopentadienylphosphid/ Phosphinocyclopentadienide via Cyclopentadienylphosphide
Authors: Schmidpeter Alfred , Zirzow Karl-Heinz
Published: March 2015

Lithiumorganyls RLi (R = Me, Bu, Ph) add to (PhP)5 in successive degradation and disproportionation equilibria depending on the ratio of the reactants. At -70 °C (R = Me) disproportionation is blocked and (PhP)4R- and (PhP)3R- can be detected. With excess RLi m onophosphides PhPR- are formed.

CpNa with the help of a crown ether degrades (PhP)5 or substitutes cyanide from PhPCN- to give an equilibrium mixture of (PhP)nCp- anions, which stabilize by proton shifts: In case of n = 1 and 2 a shift from the Cp unit to the terminal phosphorus results in the formation of the phenylphosphino- and diphenyldiphosphino-cyclopentadienide anion, in case of n = 3 two proton shifts within the Cp unit result in a cyclopenteno-l,2,3-triphospholene allylic anion.
Lactamacetale als potentielle Enamin-Synthone in Heterocyclensynthesen, 4. Mitteilung Einstufen-Synthese des γ-Carbolingerüsts durch Diels-Alder-Reaktion von Indol-„Keten-N,O-acetalen“/ Lactam Acetals as Potential Enamine Synthons in Heterocyclic Synthesis, 4th Communication. One Step Synthesis of the γ-Carboline Frame via Diels-Alder Reaction of Indol-“Ketene-N.O-Acetals”
Authors: Möhrle Hans , Dwuletzki Heinz
Published: March 2015

2-Alkoxy-indoles 2a, b can be regarded as cyclic ketene-N.O -acetals. Their regiospecific [4+2]- Diels-Alder reaction with inverse electron demand with the triazine 3 yield in a one step addition the γ-carboline (4).
Phasendiagramme von Systemen, bestehend aus Aluminiumhalogeniden und Pyridinium-hydrohalogeniden, II. Das Phasendiagramm des Systems Aluminiumbromid–Pyridiniumbromid/ Phase Diagrams of Aluminium Halide –Pyridinium Halide Systems, II. Determination of the Phase Diagram Aluminiumbromide – Pyridiniumbromide
Authors: Seemann Gerd , Hensen Karl
Published: March 2015

A phase equilibrium study of the system aluminiumbromide and pyridiniumbromide has been carried out. The phase diagram of the system indicates the existence of three congruently melting com pounds of the molar ratio AlBr3/PyHBr 1:1, 1:3, 2 :3 and one incongruently melting compound of the molar ratio 1:2 and is therefore similar to the AlCl3-PyHCl system [1].
Dialkylamino-phenyldi- und -triphosphide aus dem (PhP)5-Abbau mit Alkaliamiden / Dialkylamino-phenyldi- and -triphosphides from the Degradation of (PhP)5 by Alkali Amides
Authors: Zirzow Karl-Heinz , Schmidpeter Alfred
Published: March 2015

(PhP)5 and lithium dialkylamides in tetrahydrofuran form equilibrium mixtures of lithium aminophenylphosphides (PhP)nNR- with n = 3 and (mainly) 2. The monophosphides (n = 1) are not formed; it is concluded that they are generally unstable, decomposing to aminodiphosphides and cyclophosphines. Alkylation of an equilibrium mixture gives 1-alkyl-2-dialkylamino-diphenyl- diphosphines which, however, are thermally unstable. (PhP)5 degradation equilibria using differ­ent anionic nucleophiles are compared.
Synthese und Struktur bicyclischer arsenhaltiger Schwefel-Stickstoff-Metallkomplexe / Synthesis and Structure of Bicyclic Sulphur Nitrogen Metal Complexes Containing Arsenic
Authors: Edelmann Frank , Spang Claudia , Noltemeyer Mathias , Sheldrick George M. , Keweloh Nayla , Roesky Herbert W.
Published: March 2015

(PhAsNSN)2 (1) reacts with M(CO)4(C7H8) (M = a Cr. b Mo) to yield (PhAsNSN)2M(CO)4 (2). 2a and 2b are dark red air stable complexes. 2b was characterized by X-ray diffraction. Crystals of 2b are monoclinic, space group C2/c, with a = 2884.7(4). b = 1166.2(2), c = 1344.1(2) pm, fβ = 104.81(2)° and Z = 8. The molecule exhibits approximate mm (C2v) symmetry with mean bond lengths: Mo-As 255.1. Mo-C 201.8. As-N 186.2 and S -N 152.8 pm.
Model Substances for Electro-optical and Dielectric Studies, Part I Synthesis and Structure of 1,4-Bis(4'-dimethylamino-3',5'-dicyanophenyl)bicyclo[2.2.2]octane
Authors: Detzer Norbert , Burkhard Oswald , Schaffrin Heinz , Liptay Wolfgang
Published: March 2015

A synthesis for a new 1,2,6-donor-acceptor-substituted chromophoric benzene system is given. This chromophore is incorporated in a bicyclo[2.2.2]octane system to build up model compounds for electro-optical and dielectrical studies. Furthermore a preparative convenient route to derivatives of 1,4-bis(diphenyl)bicyclo[2.2.2]octane is worked out. The structures of the new compounds are proven by spectroscopical means.
Ein Derivat des 1λ5,3λ5,5λ3-Triphosphabenzols / A Derivative of 1λ5,3λ5,5λ3-Triphosphabenzene
Authors: Fluck Ekkehard , Becker Gerd , Neumüller Bernhard , Kneb Robert , Heckman Gemot , Riffel Heinz
Published: March 2015

The title compound was prepared by reacting 1,1,3,3-tetrakis(dimethylamino)-1λ5,3λ5-diphosphete with 2,2-dimethylpropylidynephosphane and characterized by NMR spectra and X-ray structure analysis.
Zur Kenntnis der hochsten Hydrate der Schwefelsaure: Bildung und Struktur von H2SO4 ·6,5 H2O und H2SO4 · 8 H2O [1] / On the Highest Hydrates of Sulfuric Acid: Formation and Structure of H2SO4-6.5 H2O and H2SO4 · 8 H2O [1]
Authors: Mootz Dietrich , Merschenz-Quack Angelika
Published: March 2015

The phase diagram of the system sulfuric acid-water in the range 80-100 mol % H20 was reinvestigated by low-temperature DTA and X-ray powder diffraction. The results are compared with other studies in the literature. The crystal structures of the hydrates H2SO4 · 6.5 H2O. melting incongruently at -54 °C. and H2SO4 · SH2O (metastable) were determined to be those of oxonium salts. (H5O2)(H7O1)SO4 ·1.5 H2O and (H5O2)2SO4 · 4 H2O, respectively.
Substitutionsreaktionen am N-[1-Chlor-2,2,2-trifluor-1-(trifluormethyl)ethyl]-dimethyIformamidin / Substitution Reactions with N-[1-Chloro-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]-dimethylformamidine
Authors: Grützmacher Hansjörg , Roesky Herbert W. , Noltemeyer Mathias , Sheldrick George M.
Published: March 2015

It is difficult to achieve nucleophilic attack on a carbon atom bonded on two trifluoromethyl groups. However, N-[1-chloro-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]-dimethylformamidine (1) reacts readily with H2O, MeOH, EtSH and P(OMe)3 even under mild conditions to form products 2, 3, 4 and 5. The reaction between 1 and Ph2PH is complex but leads in nearly quantitative yield to N-[2,2,2-trifluoro-1-(trifluoromethyl)ethyl]-dimethylformamidinium chloride 6 which has been characterized by an X-ray structure analysis. A reaction mechanism is proposed.
Natürliche Allergene, I. Das Auftreten von Falcarinol und Didehydrofalcarinol in Efeu (Hedera helix L.) / Natural Allergenes. I. The Occurrence of Falcarinol and Didehydrofalcarinol in Ivy (Hedera helix L .)
Authors: Bruhn Gabriele , Faasch Holger , Hahna Holger , Hausen Björn M. , Bröhan Johann , König Wilfried A.
Published: March 2015

From common ivy Hedera helix, subsp. helix and from Hedera helix, subsp. canariensis the highly unsaturated CI7-alcohols falcarinol (1) and the so far unknown didehydrofalcarinol (2) [(3R)-heptadeca-1,9(Z),11(Z),16-tetraene-4,6-diyne-3-ol] was isolated and its structures iden­tified by mass spectrometry and NMR. The (R)-configuration of falcarinol and didehydrofalcarinol was determined after catalytic hydrogenation to 3-heptadecanol by enantioselective capillary gas chromatography. Falcarinol and didehydrofalcarinol effect sensibilization and allergic skin reactions in minute concentrations.
Pilzfarbstoffe, 54 [1] / Fungal Pigments, 54 [1]
Authors: Jägers Elisabeth , Hillen-Maske Elisabeth , Steglich Wolfgang
Published: March 2015

Fruitbodies of the basidiomycete Boletopsis leucomelaena contain the leuco-peracetates of thelephoric acid and cycloleucomelone (3 and 4, respectively). The latter compound is accom­panied by a series of analogues, containing five, four, and three acetyl residues. The properties of Akagi’s “leucomelone” (1) and “protoleucomelone” (2) correspond to those of cycloleucomelone (7) and its leuco-peracetate 4.
Pilzfarbstoffe, 55 [1] / Fungal Pigments, 55 [1]
Authors: Jägers Elisabeth , Hillen-Maske Elisabeth , Schmidt Holger , Steglich Wolfgang , Horak Egon
Published: March 2015

Fruit-bodies of Anthracophyllum species contain acetates of cycloleucomelone, cyclovariegatin and atromentin in high concentrations. The cycloleucomelone derivatives are responsible for the green colour reaction with aqueous alkali both on surface. Cyclovariegatin has been synthesized via pyrandione intermediates.
Inhaltsstoffe aus Pseudocalymma elegans (Vell.) Kuhlm. 1. Isolierung von Allantoin, Lamiid und Sorbarin / Ingredients from Pseudocalymma elegans (Vell.) Kuhlm. 1. Isolation of Allantoin, Lamiide, and Sorbarin
Authors: Krebs Hans Chr.
Published: March 2015

Allantoin, the iridoid glucoside lamiide, and the flavonoide compound sorbarin could be isolated from the methanolic extract of the poisonous brazilian plant Pseudocalymma elegans. NMR data of lamiide, of its penta- and hexaacetate as well as of sorbarin are discussed.
Synthese und Bestimmung der absoluten Konfiguration von 2-Hydroxy-12-methyltridecansäure [1] / Synthesis and Absolute Configuration of 2-Hydroxy-12-methyl Tridecanoic Acid [1]
Authors: Balzer Th. , Budzikiewicz H.
Published: March 2015

The synthesis of racemic 2-hydroxy-12-methyl tridecanoic acid is described. The absolute configuration of the two enantiomers has been determined by the method of Dale and Mosher.
Die Struktur des PrCl3 bei verschiedenen Temperaturen / The Structure of PrCl3 at Different Temperatures
Authors: Gunsilius Harald , Borrmann Horst , Hettich Bernhard , Müller Reinhold , Simon Arndt , Urland Werner
Published: March 2015

Structural investigations on PrCl3 were performed from room temperature down to 40 K (powder) and from room temperature down to 83 K (single crystal). Special interest was focussed on the changes of the coordination geometry of the Pr3+-ion.
Vierkernige Molybdän-Schwefel-Cluster mit Dithiophosphinatoliganden / Tetranuclear Molybdenum-Sulfur-Clusters with Dithiophosphinato Ligands
Authors: Keck Helmut , Kruse Andreas , Kuchen Wilhelm , Mathow Jürgen , Wunderlich Hartmut
Published: March 2015

Tetranuclear clusters Mo4S4(R2PS2)6 (4) (a: R = Et, b: R = Pr) with cubane-like cores are conveniently obtained by reacting equimolar quantities of Mo3S4(Et2PS2)4, Mo(CO)6 and R2P(S)-S-S-P(S)R2. 31P NMR and MS data of 4 are reported and the magnetic properties are discussed. 4a crystallizes triclinically with a = 1159.41(6), b = 1162.77(7), c = 2228.54(14) pm, α = 102.660(3), β = 98.382(4), γ = 98.546(5)°. P1̅, Z = 2. The molecule consists of a distorted Mo4S4 cubane. Each Mo atom is coordinated by six S atoms: three within the cubane, two from a bidentate and one from a chelating dithiophosphinato ligand. Two Mo -Mo distances are short- ened by the chelate to an av. of 278.6 pm, while the av. of the remaining four Mo -Mo distances is 287.9 pm.
N-Chlor-Nitrenokomplexe des Molybdäns: MoF4(NCl) und [CH3CN-MoF4(NCl)] / N-Chloro-Nitrene Complexes of Molybdenum: MoF4(NCl) and [CH3CN-MoF4(NCl)]
Authors: Fenske Dieter , Völp Karin , Dehnicke Kurt
Published: March 2015

MoF4(NCl) has been prepared as a yellow crystal powder by the reaction of diluted fluorine with MoCl3(N3S2) at room temperature. The compound is associated via fluorine bridges, according to the IR spectrum. With acetonitrile, the monomeric complex [CH3CN -MoF4(NCl)] is obtained, which was characterized by its IR and 19F NMR spectra as well as by an X-ray structure determination. Crystal data: space group Pm, Z = 2 (1068 observed, independent reflexions, R = 0.03). Lattice dimensions at -90 °C: a = 507.1. b = 704.8, c = 995.8 pm, β = 102.02°. The unit cell contains two crystallographically independent molecules [CH3CN -MoF4(NCl)], the Mo≡N-Cl groups being linear (bond angles 176°, 178°) with bond lengths MoN = 172 and NCI = 159, 162 pm. In the trans position to the MoNCl group, the nitrogen atom of the acetonitrile molecule is coordinated.
Die anti-perowskitartige Kristallstruktur von Tris[tetraquokupfer(II)]-bis[hexafluorometallaten(III)], Cu3M2F12·12H2O (M = V, Cr, Fe) / The anti-Perovskite-Like Crystal Structure of Tris[tetraquocopper(II)]-bis[hexafluorometallates(III)], Cu3M2F12 · 12H2O (M = V, Cr, Fe)
Authors: Kummer S. , Babel D.
Published: March 2015

The crystal structures of the triclinic compounds Cu3V2F12 · 12H2O (a = 750.8. b = 760.7, c = 812.2 pm, α = 91.01, β = 89.80, γ = 92.84°; Z = 1), Cu3Cr2F12 · 12H2O and Cu3Fe2F12 · 12H2O with similar cell parameters, were refined in space group P1̅ to R factors of 0.03 and less. The structure consists of planar tetraquo cations [Cu(H2O)4]2+ (average Cu-O = 196.3 pm), which become elongated octahedra by sharing fluoride ligands of [MF6]3- anions at greater distances (av. Cu-F = 231.5 pm). The resulting three-dimensional framework of corner-sharing (distorted) octahedra contains large cavities, in which another [MF6]3- anion is inserted and fixed by hydrogen bonds. The arrangement of complex ions corresponds to an anti-perovskite structure AMX3 = [MF6][MF6][Cu(H2O)4]3. The variation of distances within the octahedra (mean values V-F = 194.3, Cr-F = 191.1 and Fe-F = 193.7 pm) is discussed in connection with the length of the hydrogen bridges O-H···F (average 270 pm and 168°).
Übergangsmetallkomplexe von Diazenen, XXIII [1]. Struktur und Mößbauer-Daten bi- und tricyclischer Ferracyclen / Transition Metal Complexes of Diazenes, XXIII [1] Structure and Mößbauer Data of Bi- and Tricyclic Ferracycles
Authors: Kisch H. , Krüger C. , Marcolin H. E. , Trautwein A. X.
Published: March 2015

Mößbauer spectra of mono and dinuclear iron carbonyl complexes of three cyclic diazenes and the crystal structures of two products formed from (cis-diazene)Fe2(CO)6 and alkynes are reported. The ring size of the diazene ligand influences the stereochemistry of the cycloadducts obtained in the latter reaction; the bicyclic diazaferracycloalkene skeleton of these compounds leads to an exo- and endo-arrangement of one iron carbonyl group relative to the five- and six- membered diazene, rcspectively.
Modellreaktionen zur Bildung und Öffnung von Furanen nebeneinander unter Verwendung von Diazocarbonyl-Verbindungen / Model Reaction on Parallel Formation and Ring Opening of Furans by Means of Diazocarbonyl Compounds
Authors: Rühl Wolfgang , Bölsing Friedrich , Hofer Edgar
Published: March 2015

In a photochemical decomposition reaction of the a-Diazoketone 1 in the presence of toluene ring-opening of the adjacent furanoyl substituent occurs as well as conversion of a norcaradiene intermediate thus forming the acetylenic olefinic aldehyde 4 and the dihydrobenzofuran 3. Reaction pathways are derived from the corresponding ketocarbeneoxirene equilibrium in which surprisingly the secondary ketocarbene B-1 gives rise to the formation of the aldehyde 4! No Wolff rearrangement product could be detected.
Preparation and Crystal Structure of [TeBr3][AuBr4] · 1/2 Br2, a Compound with “Bromine of Crystallization”
Authors: Freire-Erdbrügger Cristina , Jentsch Dieter , Jones Peter G. , Schwarzmann Einhard
Published: March 2015

The reaction between elemental gold, tellurium and bromine leads to a crystalline product of empirical formula AuBr8Te. The crystal structure determination of AuBr8Te shows that it is composed of dimeric [TeBr3 · AuBr4]2 units with secondary Te···Br interactions and of isolated Br2 molecules.
Preparation and Structural Characterization of Methylmercury(II) Complexes of 5-Aza- and 6-Azauracil Derivatives
Authors: Sheldrick W. S. , Heeb S.
Published: March 2015

1:1 Methylmercury(II) complexes of the anti-tumour agent 6-azauracil (6AUH2) and its deriva­tives 6-azathymine (6ATH2). 1-methyl-6-azauracil (6AMUH) and 1-methyl-6-azathymine (6AMTH) have been isolated from aqueous solutions of CH3HgOH and the respective base. N3-Coordination was established by X-ray structural analysis for both [(CH3Hg)6 AUH] (1) (pH 6-8) and [(CH3Hg)6 AMT] (5) (pH 4-12); in addition 1H NMR data are in accordance with an identical binding site in the complexes [(CH3Hg)6AMU] (3) and [(CH3Hg)6 ATH] (4). Using an excess of CH3HgOH. 2:1 complexes with N1, N3-coordination may be prepared for both 6 AUH: and 5 AUH2 in a wide pH range (4-12 and 6-12 respectively). At pH values of 3-4 a 3:1 complex [(CH3Hg)35 AU]NO3 (7), with N1, N3, N5-coordination may be isolated: the binding sites were confirmed by X-ray structural analysis. In no case could an ionic complex with N6- coordination be isolated for a 6-azapyrimidine derivative. The binding preferences of the bases are discussed in the light of MNDO calculations.
Darstellung und Oxidation von 2-(2,5-Dihydroxy-phenyl)-ethylamin-Derivaten, II / Synthesis and Oxidation of 2-(2,5-Dihydroxyphenyl)-ethylamine Derivatives, II
Authors: Kuckländer Uwe , Bastian Udo
Published: March 2015

2,5-Dihydroxyphenylethylamine derivatives 8a,b; 14; 19a,b and 25a,b,c are synthesized and oxidized to indole 9a, indolines 15 and 18a,b as well as 24a,b,c. Quantitative oxidation of hydroquinones yields the 2-(aminoethyl)quinones 30a as free base and 30d-f; 27a,b and the hydrochlorides 28a,b. Quinone 30a is reduced to indoline 29 and acetylated to 3-acylindole 32, transformed by heating to indole 23 and in acetic acid to the dimeric indole 31. 32 is synthesized unequivocally from 33 and 34. The course of the reaction is discussed and the formation of indolines is explained by cyclisation of a semiquinone precursor (43).
Modellreaktionen zur Plumbagin-Synthese, 2. Mitteilung 5-Amino-1-naphthol als Startkomponente / Model Reactions for Plumbagin Synthesis, 2nd Communication 5-Amino-1-naphthol as Starting Compound
Authors: Möhrle Hans , Folttmann Hubertus
Published: March 2015

The aminomethylation of 5-amino-1-naphthol (1) and 5-acetamido-1-naphthol (9) is examined. While the hydrogenolysis of the phenol Mannich bases derived from 1 cannot be accomplished, the derivatives of 9 react easily. The oxidation of the 2-methylphenol compounds 5 and 18 to the corresponding quinones may performed with Fremy's salt. The following transforming of the amino to the hydroxy group by nitrosylsulfuric acid succeeds with small yield only.
Der 2,4,6-Triisopropylbenzolsulfonyl(Tip)-Rest, eine neue Schutzgruppe für die Guanidinofunktion von Arginin / The 2,4,6-Triisopropylbenzenesulfonyl Residue, a New Protecting Group for the Guanidino Function of Arginine
Authors: Echner Hartmut , Voelter Wolfgang
Published: March 2015

The 2.4.6-triisopropylbenzenesulfonyl group is introduced in high yield into the guanidino function of arginine by the reaction of Na-protected arginine with 2.4.6-triisopropylbenzene-sulfonyl chloride. This protecting group was found to be cleaved by commonly used reagents used in peptide synthesis like methanesulfonic, trifluoromethanesulfonic acid or mixtures of tri-fluoroacetic with methanesulfonic or trifluoromethanesulfonic acid.
Acetalisierte Formylmangan-Komplexe / Acetals of Formyl Manganese Complexes
Authors: Löwe Christiane , Huttner Gottfried , Zsolnai Laszlo , Berke Heinz
Published: March 2015

Acetal complexes of the type (OC)5 MnCH(XR)2 , RX = PhO (1a), (RX)2 = 1,2-dioxybenzene (1b), (RX), = S-(CH2)3-S (2) and

(5) were synthesized. Glyoxyloyl acetal derivatives (OC)5 MnC(O)CH(XR)2, RX = PhO (3a), (RX)2 = 1,2-dioxybenzene (3b), (RX)2 = S-(CH2)3-S (4) were obtained by the action of NaMn(CO)5 upon the corresponding acid chlorides or anhydrides, la can be transformed to 3a by CO insertion, 1a has been characterized by an X-ray structure determination.
Darstellung und Struktur des Bis(triphenylarsoranyliden)ammoniumchlorids / Preparation and Structure of Bis(triphenvlarsoranylidene) Ammonium Chloride
Authors: Roesky Herbert W. , Bertel Nobert , Edelmann Frank , Noltemeyer Mathias , Sheldrick George M.
Published: March 2015

The reaction of Ph3AsCl2 (1) and N(SiMe3)3 (2) yields [Ph3As-N-AsPh3]+Cl (3) as a crystal­line white solid, soluble in CH3OH and acetone. 3 might be used to stabilize unusual anions. It crystallizes as a 1:1 toluene adduct in the space group C2/c with a - 1585.3(3). b = 1058.7(2). c = 2266.3(4) pm. β = 94.40(2)° and Z = 4. The cation in 3 lies on a crystallographic two-fold axis with As-N-As 123.9(1)°. As-N 174.9(3). and As-C 196.7(5). 197.6(5). 193.2(5) pm.
Eine schnelle Methode zur quantitativen Abtrennung von Chlor und Brom aus sauren wäßrigen Lösungen / A Rapid Method for the Quantitative Elimination of Chlorine or Bromine from Aqueous Acidic Solutions
Authors: Baumgärtner Wolfram , Gawargious Youssef A. , Brodersen Klaus
Published: March 2015

The quantitative elimination of chlorine and bromine from acidic aqueous solutions was achieved through extraction with a dilute solution of styrene in CCl4 .
Na3OCl und Na3OBr, die ersten Alkalimetallchalkogenidhalogenide / Na3OCl and Na3OBr, the First Alkali Metal Chalcogenide Halides
Authors: Sabrowsky Horst , Paszkowski Karin , Reddig Dagmar , Vogt Petra
Published: March 2015

The colourless compounds Na3OCl and Na3OBr have been prepared and characterized by X-ray diffraction techniques. Na3OCl crystallizes in a cubic primitive lattice with a = 450.0(3) pm (Z = 1). Na3OBr is isotypic with Na3OCl and its lattice constant is a = 457.3(5) pm. The structures are related to the anti-perowskitetype
Neue 1320637-Verbindungen / New 1320637 Compounds
Authors: Range Klaus-Jürgen , Handrick Karin
Published: March 2015

New quaternary compounds AgIn2X3Y (X = Se, Te; Y = Br, I) could be synthesized from AgY-In2X3-mixtures at atmospheric pressure. The crystal structures are defect-wurtzite (AgIn2S3Br) or defect-zinc-blende (AgIn2Te3Br, AgIn2Te3I). A transformation to high-pressure phases with spinel structure (AgIn2Se3Br, AgIn2Se3I) or defect-NaCl-structure (AgIn2Te3Br, AgIn2Te3I) takes place at 20 and 40 kbar.,respectively. AgIn2S3I with spinel structure could by synthesized from AgI and In2S3 at 40 kbar, 500 °C
Darstellung und [1+4]-Cycloaddition von Methylthio-chlorophosphanen RP(Cl)SMe (R = Me, Et, Ph) / Preparation and [1+4]-Cycloaddition of Methylthio-chlorophosphanes RP(Cl)SMe (R = Me, Et, Ph)
Authors: Apitz Jörg , Grobe Joseph , Le Van Due
Published: March 2015

The methylthio-chlorophosphanes RP(Cl)SMe [R = Me (1). Et (2). Ph (3)] are prepared in good yields (62-65%) by condensation reactions of the corresponding dichlorophosphanes RPC12 with methanethiol in the presence of trimethylamine (molar ratio 1:1:1). 1 and 3 have been used to produce 3-phospholene sulfides in a one-pot process by reaction with 1,3-dienes at 70 to 100 °C. Reaction proceeds via [1+4]-cycloadducts, which in suitable cases can be isolated and used for the preparation of the corresponding 3-phospholene oxides. New compounds were characterized by elemental analysis and spectroscopic investigations (NMR. MS).
Struktur eines Homoborirens / Structure of a Homoborirene
Authors: Pues Christine , Baum Gerhard , Massa Werner , Berndt Armin
Published: March 2015

Trapping of methyleneborane 7a with 3-hexine yields the stable 1,2-dihydroborete 1a . Strong folding (148.8°) along the 1,3-diagonal. the short 1.3-distance (191.5 pm), a lengthened 3,4- and a shortened 1,4-bond prove the homoborirene nature of 1a.
Darstellung von Alkylmethylphenylphosphanen nach der Methode von Hewertson und Watson / Preparation of Alkylmethylphenylphosphines by the Method of Hewertson and Watson
Authors: Wolfsberger Werner
Published: March 2015

The reaction of C6H5(CH3)PNa with some alkyl halides in liquid ammonia was studied. The resulting phosphines were characterized by elemental analyses, NMR spectra, and by the reaction with trimethylsilyl azide giving trimethylsilylimino triorganophosphoranes.
trans-4-Phenyl-3-buten-2-one from the African Harvester Ant Messor galla (Mayr) (Hymenoptera: Formicidae)
Authors: Olagbemiro T. O. , Sani K. M. , Lajide L. , Agoh M. O. , Staddon B. W. , Chukwu C. E.
Published: March 2015

By gas chromatography mass spectrometry and synthesis of authentic standard, trans-4-phenyl-3- buten-2-one for the first time as well as known hydrocarbons have been identified in the Dufour′s gland secretion of the African harvester ant Messor galla (Mayr).
Podanden, Coronanden und Kryptanden als neue Komplex-Liganden für Photoelektronentransfer-Reaktionen Synthese und erste photophysikalische Studien / Podands, Coronands and Cryptands as New Complex-Ligands in Photoeleetron Transfer Reactions Synthesis and Photophysical Studies
Authors: Dürr Heinz , Zengerle Klaus , Trierweiler Hans-Peter
Published: March 2015

Podands, coronands and cryptands containing 2,2′-bipyridine-units were synthesized. These Compounds can be used as ligands in Ru(II)-polypyridinecomplexes. This new route principally allows the preparation of tris-heteroleptic complexes using the appropriate cryptands. Ru(II)- polypyridines RuL3
2+ (e.g. Ru(bpy)3
2+) are interesting as sensitizers in photochemical water cleavage. Compared to Ru(bpy)3
2+, the photoanationrate should be reduced in the Ru(cryp)2+ complex.
Schwingungs-und Elektronenspektren der bindungsisomeren Hexakis(thiocyanato(N)-thiocyanato(S))-osmate(III) und (IV) / Vibrational and Electronic Spectra of Bond-Isomeric Hexakis(thiocyanato(N)-thiocyanato(S))osmates(III) and (IV)
Authors: Bütje K. , Preetz W.
Published: March 2015

Well-resolved IR and Raman spectra of the two sets of all 10 isomeric complexes [Os(NCS)n(SCN)6-n]3-/2-, n = 0-6, have been recorded. For both series, νCS(N) > νCS(S) and δNCS > δSCN; for the Os(III) complexes, vCN(N) ~ vCN(S) and vOsN ≥ vOsS while for the Os(IV) compounds, vCN(N) < vCN(S) and vOsN ~ vOsS. The vibrational spectra of the n = 0 and n = 6 members of both sets are assigned according to D3d and Oh point symmetry, respectively. For the mixed linkage isomers the band pattern is strongly influenced by pseudo-octahedral coupling wherever frequencies of N- and S-bonded groups coincide. The metal-ligand stretching region is therefore assigned according rather to pseudo-Oh, pseudo-D3d and pseudo-D4h symmetry than to D4h, C4v, C3v and C2v microsymmetry. The charge-transfer spectra of both series are similar, showing a parallel hypsochromic shift with increasing n value. Upon oxidation, a bathochromic shift of the CT bands by an average of 5400 cm-1 is observed, and the intensity increases by a factor 2-2.5. Weak absorptions in the near infrared region are assigned to intraconfigurational transitions.
Metall-Komplexe mit S4N4 -Liganden: Die Strukturen von zwei Komplexen der Zusammensetzung [TiCl4(S4N4)]2 / Metal Complexes with S4N4 Ligands: The Structures of Two Complexes of Composition [TiCl4(S4N4)]2
Authors: Thewalt Ulf , Holl Konrad
Published: March 2015

Slow reaction of TiCl4 with S4N4 in CH2Cl2/CCl4 produces a mixture of two crystalline dinuclear complexes of composition [TiCl4(S4N4)]2. Crystal data for the orange-yellow α-isomer: mono­clinic, space group P21/n with a = 11.608(3) Å. b = 8.304(3) Å, c = 10.938(5) Å, β = 101.06(4)° and Z = 2. Crystal data for the red-brown β-isomer: monoclinic, space group P21/c with a = 11.220(2) Å, b = 13.868(2) Å, c = 14.839(4) Å, β = 106.18(2)° and Z = 4. Crystal structure analyses reveal that the S4N4 molecules in the α-form act as 1,3-N,N′-bonded bridging ligands and in the β-form as N-bonded monodentate ligands.
ESCA Studies of N,N′-Thiobisamines and of Some of its Chromium Carbonyl Complexes
Authors: González G. , Díaz C. , Binder H.
Published: March 2015

The X-ray photoelectron spectra of some N,N′-thiobisamines and of two of its complexes with Cr(CO)5 have been studied. The S(2p) binding energies are found to correlate with the effective nuclear charge on the sulfur atom as well as with the double bond character of the S-N linkage. The effect of the coordination on the N(1s) and S(2p) binding energies agree with sulfur coordination as well as with a π acceptor behaviour characteristic for thiobisamine ligands.
Darstellung und Kristallstruktur von Cäsiumhydroxid mit Methanol CsOH · CH3OH / Properties and Crystal Structure of Cesium Hydroxide with Methanol CsOH · CH3OH
Authors: Marx Rupert
Published: March 2015

Cesium hydroxide methanol, CsOH·CH3OH, was obtained by recrystallising CsOH·H2O in a mixture of liquid ammonia and methanol in sealed quartz ampoules. The colourless, air sensitive crystals are hexagonal (space group P63/m) with a = 1362 pm, c = 430 pm, Z = 6. A structural model derived by Patterson methods was refined to R = 0.033. The structure comprises of trigonal prismatic columns of Cs+ and hydrogen bonded chains of OH- and CH3OH along the c-axis. This leads to the tricapped prisms filled with Cs+ and hydrophobic channels formed by the CH3 groups.
Benzoatokomplexe des Eisens und Cobalts Synthese und Eigenschaften von Fe3(C6H5COO)4(acac)2, Fe(C6H5COO)2 und CO(C6H5COO)2 , Kristallstruktur von Fe3(C6H5COO)4(acac)2 und Co(C6H5COO)2 / Benzoato Complexes of Iron and Cobalt Synthesis and Properties of Fe3(C6H5COO)4(acac)2, Fe(C6H5COO)2 and Co(C6H5COO)2, Crystal Structure of Fe3(C6H5COO)4(acac)2 and Co(C6H5COO)2
Authors: Spohn Martin , Strähle Joachim
Published: March 2015

The reaction of iron(III) acetylacetonate with molten benzoic acid yields Fe(C6H5COO)2 (2) besides small amounts of Fe3(C6H5COO)4(acac)2 (1), whereas cobalt(III) acetylacetonate or cobalt(II) carbonate quantitatively yield Co(C6H5COO)3 (3). Complex 1 forms triclinic red crystals with the space group PI and the lattice constants a = 1016.0(3) pm, b = 1099.9(2) pm, c = 969.8(2) pm, α = 92.68(2)°, β = 105.67(2)°, γ = 117.57(2)°, Z = 1. 3 is obtained as monoclinic violet needles with the space group C2/c and the lattice constants a = 1739.2(4) pm, b = 1413.8(3) pm, c = 1045.3(3) pm, β = 96.26(2)°, Z = 8. 3 consists of polymeric chains with a zigzag arrangement of the cobalt atoms (Co -Co = 314.5 pm) and an octahedral coordination for Co 1 and (4+2)-coordination for Co2. The benzoato ligands act differently. One benzoate group functions as bridging ligand between adjacent metal atoms, the other acts as a four-dentate ligand by chelating one cobalt atom and bridging its neighbours. Complex 2 was not obtained in form of single crystals, but its properties as well as its IR and Mößbauer spectra suggest a similar structure as for 3. Complex 1 is also polymeric, the chain of iron atoms is nearly linear. The acetylacetonate ligand acts chelating and bridging as a four-dentate ligand, whereas the benzoate anion is only bridging neighbouring Fe atoms. The Fe atoms exhibit octahedral and trigonal bipyramidal coordination.
Über die Reaktivität von [(CH3)2N]6W2 (W≡W) gegenüber CS2/S8 und CS2/Se8. Röntgenstrukturanalyse von [(CH3)2NCS2]2W(S)(S2) / Reactivity of [(CH3)2N]6W2 (W≡W) Towards CS2/S8 and CS2/Se8. X-Ray Structure Analysis of [(CH3)2NCS2]2W(S)(S2)
Authors: Ziegler Manfred L. , Blechschmitt Klaus , Bock Harald , Guggolz Ernst , Korswagen Richard P.
Published: March 2015

In this paper we report two improved preparation methods for [(CH3)2N]6W2 (W≡W) (1), one starting from WCl4 (yield 51%), and a second one starting from W2C16(THF)4 (ca. 60% yield). We have studied the reactions of 1 with different nucleophiles, among them triphenylalkylidenphosphoranes (like Ph3P=CH2 and Ph3P=CHPh·LiCl; Ph = phenyl), sulfur and CS2 .

1 reacts with S8 and CS2 in hexane to yield the two new compounds (Me2NCS2)2WS(S2) (4) and W(CS2H)(Me2NCS2)2 (5), both containing dithiocarbamato ligands formed by insertion of CS2 into the W-N bond. The two mononuclear compounds were characterized spectroscopically, in the case of 4 an X-ray diffraction structure analysis was performed. The reaction of 1 with Se and CS2 , leads to the compounds 4, (Me2NCS2)2W2S4 (6) and [(Me2N)2C]CS2 (7), which were also characterized spectroscopically. No Se-containing compounds could be isolated.

4 crystallizes monoclinically, C5
2h-P21/n, with a = 648.6(3), b = 1346.7(6) and c = 1745.9(7) pm, β = 91.85(3)°, V = 1524x106 pm3 , Z = 4. The structure of the seven-coordinate tungsten compound is discussed and compared to complexes with similar ligands and geometry.