bluuebunny/crossref_metadata_2025 huggingface dataset:
Synthesis and Crystal Structure of Tris- [3,5-bis(trifluoromethyl)phenyl]arsine
Authors: Dietzel Pascal D. C. , Jansen Martin
Published: August 2018

The title compound, As[C6H3(CF3)2]3, has been synthesised by Grignard reaction from arsenic trichloride and 3,5-bis(trifluoromethyl)phenylmagnesium bromide. It crystallises in the triclinic space group P1̅ with two formula units in the asymmetric unit. The most prominent feature of the crystal structure is the protrusion of a phenyl group of one molecule into the cavity at the base of the pyramid of a second molecule. The crystal structure is then built up by densely packing these units of interlocked molecules to form columns, which are arranged in parallel in a distorted hexagonal pattern
Orthoamide, LX [1]. N,N,N’,N’-Tetraformylhydrazin – ein breit anwendbares Formylierungsmittel für aromatische Verbindungen / Orthoamide, LX [1]. N,N,N’,N’-Tetraformylhydrazine – a Formylation Agent for Aromatic Compounds of Wide Scope
Authors: Kantlehner Willi , Haug Erwin , Scherr Oliver , Stoyanov Edmont V. , Mezger Jochen , Ziegler Georg
Published: August 2018

Keywords

The reagent system formed from N,N,N’,N’-tetraformylhydrazine (3) and aluminum chloride allows the formylation of aromatic compounds. The scope of the method is comparable with the Olah formylation and the Groß-Rieche procedure, since benzene and fluorobenzene can be formylated. Two formyl groups are transferred from 3 to the aromatic nuclei when a molar ratio 4:1:4 (aluminum chloride/3/aromatic compound) is chosen.
Fries Rearrangement of Aryl Formates Promoted by BCl3. Mechanistic Evidence from 11B NMR Spectra and DFT Calculations
Authors: Bagno Alessandro , Kantlehner Willi , Kreß Ralf , Saielli Giacomo
Published: August 2018

The Fries rearrangement of model aryl formate esters, promoted by boron trichloride, has been investigated by means of NMR spectroscopy (both experimental and computational) and by DFT calculations. Firstly, the 11B NMR chemical shifts of a series of model boron compounds have been predicted by GIAO-B3LYP/6-31G(d,p) calculations, in order to make predictions of the chemical shifts of transient reaction intermediates observable by 11B NMR. Such 11B spectra for the reaction of two esters (phenyl and 3-methyoxyphenyl formates) have been obtained, and are found to follow different patterns which can be rationalized on the basis of computed chemical shifts. Secondly, DFT calculations (B3LYP/6-31G(d,p) level) have been employed to investigate several mechanistic pathways of the rearrangement of phenyl formate. It is found that the pathways leading to the lowest activation energies are those in which formyl chloride is generated from a complex between phenyl formate and BCl3, which then acts as the formylating agent.
The Coupling-Isomerization Approach to Enimines and the First Sequential Three-Component Access to 2-Ethoxy Pyridines
Authors: Dediu Oana G. , Yehia Nasser A. M. , Müller Thomas J. J.
Published: August 2018

The coupling-isomerization reaction (CIR) of electron-deficient halides 1 with N-[1-(hetero)arylprop-2-ynyl] tosyl amides 2 leads to the formation of N-tosyl enimines 3, in good to excellent yields. These electron deficient heterodienes are perfectly suited for Diels-Alder reactions with inverse electron demand. In the sense of a one-pot reaction a three-component CIR-cyclocondensation sequence of 1, 2a, and diethyl ketene acetal gives rise to the formation of 2-ethoxy 6-(p-anisyl)pyridines 4 in moderate to good yields.
Reactivity of Tetracyclic Iminium Salts of the Benzo[f]pyrido[2,1-a]- isoindole and Azepino[2,1-a]benzo[f]isoindole Type, with a Preliminary Analysis of their Interactions with Nucleic Acids*
Authors: Maas Gerhard , Herz Hans-Georg , Scheppach Elke , Susanne Barbara , Schneider Hans-Jörg
Published: August 2018

Hydride reduction of the tetracyclic isoindolium salt derivatives 2a - c yields the neutral isoindole derivatives 9-chloro-1,2,3,4,6,6a,7,12b-octahydrobenzo[ƒ]pyrido[2,1-a]isoindole (3a), 4,4a,5,7,8,9,10,10a-octahydropyrido[2,1-a]thieno[3,2-f]isoindole (3b), and 10-chloro- 2,3,4,5,7,7a,8,13b-octahydro-1H-azepino[ƒ]pyrido[2,1-a]isoindole (3c). Oxidation of 3a with selenium dioxide is accompanied by a ring transformation and yields 8-chloro-5,5a,6,12-tetrahydrobenzo[g]pyrrolo[1,2-b]isoquinolin-12-one (4). Deprotonation of isoindolium salt derivatives 2a,c,d yields cyclic enamines which undergo ring expansion with dimethyl acetylenedicarboxylate resulting in compounds with the 4,5,6,8,8a,9-hexahydroazocino[2,1-a]benzo[ƒ]isoindole (6a), 4,6,7,9,9a,10-hexahydro-5H-azonino[2,1-a]benzo[ƒ]isoindole (6c) and 4a,5,7,8,9,10-hexahydro- 4H-azonino[2,1-a]thieno[3,2- ƒ]isoindole (6d) skeleton. Interactions of 2 with double-stranded nucleic acids are characterized by relatively large NMR upfield shifts (0.25 ppm) and signal broadening (by about 45 Hz) of aromatic ligand signals, indicating at least partial stacking with nucleobases. Rather small effects are observed, however, in melting point and viscosity increase with double strands; this is tentatively ascribed to competitive interactions with unfolded polymer parts.
Tris-N-(N′,N′,N″,N″-tetramethylguanidyl)phosphine Oxide – Synthesis and Reaction with Acids
Authors: Freytag Matthias , Plack Volker , Jones Peter G. , Schmutzler Reinhard
Published: August 2018

The phosphoryl compound (O:)P(TMG)3 (TMG = N’,N’,N”,N”-tetramethylguanidyl) (6) was synthesized during attempts to obtain the potentially very basic (but still unknown) compound P(TMG)3 (1). Its reaction with HCl resulted in the triply protonated species 7. The crystal structure of compound 7 was determined; it crystallizes as a bis-dichloromethane solvate. Each protonated nitrogen forms a hydrogen bond to one chloride. A series of protonation experiments was conducted in order to test the behaviour of 6 towards weak acids.
The Pd(II) Complex of a Bidentate Di(benzimidazol-2-ylidene) Ligand
Authors: Hahn F. Ekkehardt , Fehrena Thorsten von , Wittenbecher Lars , Fröhlich Roland
Published: August 2018

The pale yellow palladium(II) dicarbene complex cis-[PdI2(L)], 2 (L = 1,3-bis-(3-neopentylbenzimidazol- 2-ylidene)-2,2-dimethylpropane) was synthesized by the reaction of PdI2 with an N1,N1’- 2,2’-dimethylpropane-bridged dibenzotetraazafulvalene 1 in tetrahydrofuran. The X-ray structure analysis revealed a mononuclear complex with a palladium(II) center coordinated in a slightly distorted square-planar fashion by the bidentate carbene ligand and two iodo ligands.
Synthesis and Characterization of Diarylthiourea Derivatives of Tungsten Carbonyl
Authors: Srivastava Amar , Shrimal A.K. , Nath Amar
Published: August 2018

Reactions of five sym-diarylthioureas (L), viz,, sym-diphenylthiourea (dptu), sym-di-o-tolylthiourea (dottu), sym-di-p-tolylthiourea (dpttu), sym-di-o-anisylthiourea (doatu) and sym-di-α- naphthylthiourea (dαntu) with W(CO)6 have been performed both by reflux and ultra-violet irradiation methods in which only monosubstituted products [(L)W(CO)5] are obtained. Several mixed ligand tungsten carbonyl derivatives, viz., [(o-phen or 2,2’-bipy)(L)W(CO)3] and [(Ph3P or Ph3As)(L)W(CO)4] have also been synthesized. Halogenation of [(L)W(CO)5] yielded heptacoordinated [(L)W(CO)4X2] (X = Br or I). The complexes have been characterized by microanalytical data, conductivity and IR measurements. The C-O stretching force constants and CO-CO stretch-stretch interaction constants of [(L)W(CO)5] derivatives have also been evaluated from the IR spectra.
A New Clerodane Diterpene and Other Constituents from Ajuga chamaepitys ssp. laevigata
Authors: Topçu Gülaçtı , Kökdil Gamze , Türkmen Zeynep , Voelter Wolfgang , Adou Eba , Kingston David G. I.
Published: August 2018

From Ajuga chamepitys ssp. laevigata, a new clerodane diterpene, ajugalaevigatic acid, has been isolated besides five known compounds, a diterpene, (13S)-15-hydroxylabd-8(17)-en-19-oic acid, a steroidal glucoside, 3-O-β -D-glucopyranosyl-stigmasta-5,25-diene, and triterpenes,α- and β -amyrin and ursolic acid. Their structural elucidation is based on NMR and MS spectroscopic analyses. For the new compound 2D NMR experiments were carried out. Ajugalaevigatic acid was tested against a panel of cytotoxic cell lines, and only found to be active against the A2780 human ovarian cancer cell line.
Interesting Behavior of Acetone under the Willgerodt-Kindler Reaction Conditions
Authors: Darabi Hossein Reza , Aghapoor Kioumars , Nakhshab Leila
Published: August 2018

A one-pot synthesis of thiomorpholides 1 - 3 is introduced. The Willgerodt-Kindler reaction of acetone with sulfur and morpholine gives selectively one of the products 1 - 4 depending upon the proper choice of the reaction condition. The formed products are strongly dependent on the experimental conditions. The pathways of the reaction toward the formation of each product are also proposed.
Syntheses and Crystal Structures of the Two New Polychalcogenides [Mn(C6H14N2)3]Se6 and [Mn(C6H14N2)3]2[C6H16N2](TeSe2)2Se
Authors: Wendland Frank , Näther Christian , Bensch Wolfgang
Published: August 2018

The solvothermal reaction of MnCl2·4 H2O, K2Se3 and Se in trans-cyclohexane-1,2-diamine (chxn) at 433 K yields dark blue crystals of [Mn(chxn)3]Se6 (1), and the reaction of MnCl2 ・4 H2O, K2Se3 and Te under similar conditions gives dark blue crystals of [Mn(chxn)3]2[H2chxn](TeSe2)2Se (2). While compound (1) crystallises in the orthorhombic space group Pbcn with the lattice parameters a = 13.7017(9), b = 19.9073(8) and c = 10.8058(5)Å , compound (2) crystallises in the monoclinic space group P21 with the lattice parameters a = 9.4396(6), b = 24.2450(2), c = 12.8170(8) Å and β =91.6(1)◦. In both structures discrete complex cations and polychalcogenide anions are found. In (1) the Se6
2− anions form a pseudo-layer arrangement with nearly rectangular pores. The complex cations are encapsulated by the arrangement of the Se6
2− anions. Some short distances between the amino groups of the ligands and the anions indicate weak hydrogen bonding. In compound (2) two independent [Mn(chxn)3]2+ and one unique H2chxn dications, two unique TeSe2
2− as well as one Se2− dianion coexist. The two complex cations exhibit different conformations. One of the two TeSe2
2− anions has the di-protonated chxn molecule in the neighbourhood and short Se···H separations indicate weak hydrogen bonding. The isolated Se2− ion is located above the ring of the di-protonated trans-cyclohexane-1,2-diamine molecule and again a short Se···H separation may be due to a weak hydrogen bond. Compound (1) decomposes in a single step when heated in an Ar atmosphere. In contrast, the thermal decomposition of compound (2) is complex and at least five different steps can be identified.
Die (1-Cyclohepta-2,4,6-trienyl)thiolato-verbrüuckten Zweikernkomplexe – Mn2(CO)8(μ2-SC7H7)2 und Mn2(CO)6(C≡NtBu)2(μ2-SC7H7)2 / The (1-Cyclohepta-2,4,6-trienyl)thiolato-Bridged Dinuclear Complexes Mn2(CO)8(μ2-SC7H7)2 and Mn2(CO)6(C≡NtBu)2(μ2-SC7H7)2
Authors: Herberhold Max , Milius Wolfgang , Liu Jinnan
Published: August 2018

The reactions of either Mn2(CO)10 (under irradiation) or Mn(CO)5X (X = Cl, Br) with di(1-cyclohepta-2,4,6-trienyl) sulfide, S(C7H7)2 (1), led to the organothiolato-bridged dimer [Mn(CO)4(μ2-SC7H7)]2 (2) in addition to ditropyl, (C7H7)2. Subsequent substitution of two carbonyl ligands in 2 for tert-butyl isocyanide gave [Mn(CO)3(C≡NtBu)(μ2-SC7H7)]2 (3). The molecular structures of the centrosymmetric dimers 2 and 3 have been determined by X-Ray crystallography. Both 2 and 3 contain a planar Mn2S2 core with the 1-cyclohepta-2,4,6-trienyl substituents in anti-position. The structural parameters of dinuclear carbonylmanganese complexes containing organothiolato or thioether bridges are discussed.
The Solid Solution TmNi1–x–yIn1+x
Authors: Lukachuk Mar’yana , Kalychak Yaroslav M. , Pöttgen Rainer
Published: August 2018

The thulium nickel indide TmNiIn forms solid solutions TmNi1−x−yIn1+x. Several samples have been prepared by arc-melting of the elements under argon. The structure of TmNiIn contains two crystallographically different nickel sites. The Ni1 atoms have a trigonal prismatic coordination by indium, while the Ni2 sites have six thulium neighbors in a trigonal prismatic arrangement. The Ni1 sites show defects in the solid solution, while the Ni2 sites have Ni2/In mixing with a maximal occupancy of 32 at.-% indium. The structures of three single crystals of solid solutions have been refined, leading to the compositions TmNi0.88In1.10 (a =747.06(7), c = 367.8(1) pm, wR2 =0.0342, 323 F2 values, 16 variables), TmNi0.80In1.16 (a= 752.94(7), c =366.5(1) pm, wR2=0.0475, 503 F2 values, 16 variables), and TmNi0.76In1.21 (a = 758.4(1), c = 366.68(7) pm, wR2 = 0.0949, 226 F2 values, 16 variables). The crystal chemical peculiarities and the differences in chemical bonding are briefly discussed.
Über die Dialkaliacetylendicarboxylate Na2(C2(COO)2)(H2O)4 und K2(C2(COO)2)(H2O) / On Dialkali Acetylenedicarboxylates Na2(C2(COO)2)(H2O)4 and K2(C2(COO)2)(H2O)
Authors: Billetter Heinrich , Pantenburg Ingo , Ruschewitz Uwe
Published: August 2018

From aqueous solutions containing acetylenedicarboxylic acid and Na2CO3 or KOH single crystals of Na2(C2(COO)2)(H2O)4 (P21/n, Z = 2) and K2(C2(COO)2)(H2O) (P1̅, Z = 2) were obtained by slow evaporation of the solvent. In Na2(C2(COO)2)(H2O)4 the sodium atom is co-ordinated almost octahedrally by three water molecules and three oxygen atoms of the carboxylate ligands. These octahedra are connected to layers, which are held together by hydrogen bonds. In K2(C2(COO)2)(H2O) two crystallographic distinct potassium ions exist both seven co-ordinate by oxygen atoms stemming from water molecules and carboxylate ligands. These KO7 polyhedra are linked to a threedimensional structure by the bifunctional carboxylate anions and the water molecules.
An Internally Coordinated Metalla[14]-crown-5 System with a Pentagonal-dipyramidal Coordination Geometry of the Central Titanium Atom
Authors: Unger Gesa , Erker Gerhard , Kehr Gerald , Fröhlich Roland
Published: August 2018

Treatment of the dilithiated dibenzotetraethyleneglycol reagent [(o-C6H4OLi)-(OCH2CH2)2O- (o-C6H4OLi)] (5) with TiCl4 · 2 THF gave the corresponding metal complex [{(o-C6H4O-) - (OCH2CH2)2O-(o-C6H4O-)}TiCl2] (6). The X-ray crystal structure analysis of 6 revealed that all five oxygen atoms are located in one plane and bonded to titanium in a pentagonal-dipyramidal geometry with the two chloride ligands being oriented trans to each other in the apical positions.
Protoilludane-Type Sesquiterpenes, Echinocidins A and B, from a Mycelial Culture of Echinodontium tsugicola
Authors: Shiono Yoshihito , Seto Takayuki , Kamata Manabu , Takita Chinatsu , Suzuki Shinsuke , Murayama Tetsuya , Ikeda Michimasa
Published: August 2018

Two novel protoilludane sesquiterpenoids, echinocidins A (3) and B, (4) have been isolated from an artificial liquid culture of the basidiomycetous fungus Echinodontium tsugicola and their structures clarified spectroscopically. Echinocidin A (3) accelerated primary root growth to 117% and echinocidin B to 180% of controls at a concentration of 100 ppm.
Formation of an Iron(III) Oxo Cubane Core Fe4(μ4-O)4 from FeCl3 and the Unsymmetrical Tripodal Ligand N[(CH2CH2NH2)(CH2CH2OH)(CH2CH2CH2OH)]
Authors: Hahn Ekkehardt , Jocher Christoph , Lügger Thomas
Published: August 2018

The coordination chemistry of the unsymmetric, aliphatic, tetradentate tripodal ligand N[(CH2CH2NH2)(CH2CH2OH)(CH2CH2CH2OH)] H4-1 with iron chlorides was investigated. The disodium salt of the deprotonated ligand Na2(H2-1) reacts with FeCl3 to yield a yellow precipitate which upon recrystallization from DMSO/CH2Cl2 gives red crystals of the octanuclear iron(III) complex [{FeIIICl(H2-1)}4FeIII
4(μ4-O)4Cl4] 2 ・ 4CH2Cl2 containing a central Fe4(μ4-O)4 cubane core. Crystals of 2 ・4DMF were obtained by slow oxidation of the green iron(II) complex obtained from ferrous chloride and Na2(H2-1) after recrystallization from DMF. The structure determination of 2 ・4CH2Cl2 also revealed the presence of the iron(III) oxo cubane core. The core is surrounded by four iron atoms each coordinated by η4-(H2-1)2- and Cl- ligands.
Development of A Novel Solid-State pH Sensor Based on Tin Oxide Thin Film
Authors: El-Agez Taher M. , Al-Saraj Manal R. , Abdel-Latif Monzir S.
Published: August 2018

A solid-state pH sensor was fabricated using a transparent conductive tin oxide film on a glass substrate. The coating of the glass substrate was achieved by a novel simple chemical vapor deposition (CVD) procedure. The response time of the pH sensor was substantially reduced when a thin graphite film was deposited onto the tin oxide conductive film. The sensor slope was found to increase as the temperature of the solution was increased. The performance of the sensor was investigated in the pH range from 0.3 to 11.0. A straight-line calibration graph was achieved throughout the whole range tested, especially when the solution temperature was 80 ℃. The working pH range was found to decrease on the expense of the lower range as the temperature was decreased. Results obtained by the suggested sensor compares very well with conventional pH electrodes where the square of the correlation coefficient was 0.999.
Crystal Structure and Thermal Behaviour of Er2(SeO4)3 · 8H2O
Authors: Krügermann Ina , Wickleder Mathias S.
Published: August 2018

Single crystals of Er2(SeO4)3 ・ 8H2O were obtained by dissolving Er2O3 in selenic acid. The selenate crystallizes in the monoclinic space group C2/c (Z = 4, a = 1372.8(2), b = 687.51(7), c = 1860.2(3) pm, β = 101.85(2)◦, Rall = 0.0518) and contains the Er3+ ions in eightfold coordination of oxygen atoms that belong to two crystallographically different SeO4
2− ions and to four H2O molecules. According to DTA/TG measurements and temperature dependent powder diffraction data, Er2(SeO4)3 ・8H2O decomposes in several steps yielding finally Er2O3. Er2(SeO4)3 and Er2(SeO3)3 could be identified as intermediates, and for Er2(SeO4)3 a phase transition was detected.
Synthesis, Crystal Structure and Thermal Properties of Silver(I) Bromide Ethylenediamine Coordination Polymers
Authors: Näther Christian , Beck Andreas
Published: August 2018

Reaction of silver(I) bromide with ethylenediamine (en) leads to the formation of the 1:1 compound poly[AgBr(μ2-en-N,N’)] (I). In the crystal structure the silver atoms of AgBr dimers are connected to two bridging bromine atoms and two nitrogen atoms of different en ligands. The dimers are thus connected by the ligands into layers via μ-N,N’ coordination. In the 2:1 coordination polymer poly[(AgBr)2(μ2-en-N,N’)] (II) a three-dimensional AgBr substructure occur which consists of helical AgBr chains that are connected via peripheral Ag-Br contacts into a three-dimensional network that contains large channels. The en ligands are situated in these channels bridging the Ag atoms. From solution this compound cannot be obtained as a pure phase, since compound I is always formed as the major phase. On heating the 1:1 compound I in a thermobalance the sample mass decreases slowly and several mass steps are observed, which are not fully resolved. If the reaction is stopped at 230°C, pure AgBr has formed. At 115°C only traces of compound II are found. The major phase consists of an as yet unidentified ligand poor compound.
Pt3Ga: Thermodynamics and Nonstoichiometry
Authors: Schweitzer Agnes , Huang Yongzhang , Yuan Wenxia , Qiao Zhiyu , Semenova Olga , Gehringer Friedrich , Ipser Herbert
Published: August 2018

Thermodynamic activities of gallium were measured between about 1000 and 1300 K in the nonstoichiometric intermetallic compound Pt3Ga using an emf-method based on an oxygen conducting solid electrolyte. The variation of the lattice parameter with composition was determined by powder X-ray diffraction. The results of the activity measurements are interpreted in terms of a statisticalthermodynamic model for L12-phases considering four types of point defects, i. e. anti-structure atoms and vacancies on the platinum and gallium substructures. The energies of formation of the point defects at the stoichiometric composition are estimated from a curve fitting procedure yielding Ef(PtGa) = Ef(GaPt) = 1.25 eV, assuming that Ef(VPt) = Ef(VGa) = 2.0 eV. This results in a disorder parameter α’ = 3 · 10−6 at 1173 K which means that at the stoichiometric composition 0.0012% of the gallium substructure sites are occupied by platinum atoms and 0.0004% of the platinum sites by gallium atoms at this temperature.
Reduction of 1-Hydroxyimino-1,2,3,4-tetrahydrocarbazoles by Metal and Baker’s Yeast – Syntheses of Aminocarbazole Derivatives
Authors: Danish Isravel A , Prasad Karnam J. R.
Published: August 2018

1-Hydroxyimino-1,2,3,4-tetrahydrocarbazoles (1) were reduced with zinc in acetic acid and acetic anhydride and with bakers’ yeast in an aim to synthesize 1-aminocarbazoles, but interestingly the reaction gave hitherto unknown compounds, 2-acetoxy-1-(acetylamino)carbazoles (2) and 6- [acetoxy(hydroxy)methyl]-1-hydroxylaminocarbazoles (3), respectively. A plausible mechanism for the formation of compounds 2 and 3 is proposed. All new compounds were characterised by IR, NMR, mass spectral methods and elemental analysis.
Diastereomeric Halfsandwich Rhenium Complexes Containing Thiolate and Thioaldehyde Ligands
Authors: Dilsky Stefan , Schenk Wolfdieter A.
Published: August 2018

The reaction of diastereomeric methyl rhenium complexes [CpRe(NO)(NMDPP)(CH3)] (NMDPP = neomenthyl-diphenylphosphine) and [CpRe(NO)(PAMP)(CH3)] (PAMP = phenyl-2- anisyl-methylphosphine) with thiols in the presence of HBF4 gave thiolate complexes [CpRe(NO)(NMDPP)(SCH2Ph)] and [CpRe(NO)(PAMP)(SCH2R)] (R = Ph, 4-C6H4Cl, 4-C6H4OMe, 2-C4H3O, CH3, CH=CH2). Treatment of [CpRe(NO)(PAMP)(THF)]BF4 with the thiols and Na2CO3 gave the same compounds under neutral conditions. Similarly, the reaction of the chelate complex {CpRe(NO)[κP(Ph)(Me)(CH2C4H3κS)]}BF4 with thiols and NaOEt yielded the ring-opened products {CpRe(NO)[P(Ph)(Me)(CH2C4H3S)](SCH2R)} (R = Ph, 4-C6H4Cl, 4-C6H4OMe). One of the benzylic hydrogen atoms can be abstracted with [Ph3C]BF4 to give the diastereomeric thiobenzaldehyde complexes [CpRe(NO)(PAMP)(S=CHR)]BF4 (R = Ph, 4-C6H4Cl, 4-C6H4OMe) and {CpRe(NO)[P(Ph)(Me)(CH2C4H3S)](S=CHPh)}BF4. In these products, the thioformyl group is predominantly η2(C,S) coordinated to rhenium, but in a few cases the corresponding η1(S) isomers were also detected by IR and NMR spectroscopy.
Multidentate Aminoalkoxides. Synthesis and Complexation Behavior to Lithium and Sodium
Authors: Müller Gerhard , Schätzle Torsten
Published: August 2018

The tris(dimethylaminomethyl)-substituted alcohol (R2NCH2)3COH (R = Me: 1) was synthesized by reaction of 1-chloro-2,3-epoxy-2-chloromethylpropane with a large excess of 40% aqueous HNMe2 in 95% yield as colorless liquid (b.p. 87 ­­°C/1 mbar). Similar syntheses led to the respective amino alcohols with R = Et, CH2Ph. The dimethylamino alcohol 1 was characterized crystallographically as hydrochloride salt 2. Reaction of 1 with elemental sodium in toluene gave the tetrameric alcoholate [(Me2NCH2)3CONa]4 (3) which has a heterocubane structure in the solid state. In addition to three oxygen atoms, each sodium atom is coordinated by two amino groups from two different adjacent ligands (Na-N 2.529(3)/2.628(3) Å ). Reaction of 1 with LiNMe2 afforded the lithium alcoholate which crystallized as dimeric mixed-anion aggregate [(Me2NCH2)3COLi·LiNMe2]2 (4). It has a four-rung ladder structure consisting of two four-membered Li(NMe2)LiO rings connected through a central LiOLiO ring. All ligand amino groups are lithium-coordinated (Li-N 2.117(6)/2.101(6)/2.218(6) Å) as is the amido nitrogen atom (Li-N 1.964(6)/2.027(6) Å). Reaction of 1 with LitBu in n-hexane also led to deprotonation at oxygen. In addition, in one ligand one methyl group is deprotonated, in a second one two methyl groups are lithiated leading to doubly and triply charged anions, respectively. The product crystallizes as the dimeric mixed-anion aggregate [(−H2CN(Me)CH2)(Me2NCH2)2CO−·5 Li+· (−H2CN(Me)CH2)2(Me2NCH2)CO−]2 (5) having a core of 10 Li+ cations, 4 alcoholate oxygen atoms, and 6 N(Me)-CH2
− groups.
N-Benzyl- und N-Heptyl-substituierte Tetraazacyclododecane / N-Benzyl and N-Heptyl Substituted Tetraazacyclodecanes
Authors: Schumann Herbert , Kuse Katharina , Dechert Sebastian
Published: August 2018

1,5-Bis(methylsulfonyloxi)-3-aza-3-p-toluenesulfonylamidopentane (1) reacts with 4-benzyl-1,7- bis(p-toluenesulfonyl)diethylenetriamine (2) and 4-benzyl-1,7-bis(p-nitrophenylsulfonyl)diethylenetriamine (3) and Cs2CO3 yielding 1-benzyl-4,7,10-tris(p-toluenesulfonyl)-1,4,7,10-tetraazacyclododecane (9a) and 1-benzyl-4,10-bis(p-nitrophenylsulfonyl)-7-p-toluenesulfonyl)-1,4,7,10-tetraazacyclododecane (10a), respectively. The corresponding dimers 1,13-bis(benzyl)-4,7,10,16,19,22- hexa(p-toluenesulfonyl)-1,4,7,10,13,16,19,22-octaazacyclotetracosane (9b) and 1,13-bis(benzyl)- 4,10,16,22-tetra(p-nitrophenylsulfonyl)-7,19-bis(p-toluenesulfonyl)-1,4,7,10,13,16,19,22-octaazacyclotetracosane (10b) could not be isolated but detected by mass spectroscopy. The reactions of 1 with 4-heptyl-1,7-bis(p-nitrophenylsulfonyl)diethylenetriamine (5) and Cs2CO3 results in the formation of 1-heptyl-4,10-bis(p-nitrophenylsulfonyl)-7-p-toluenesulfonyl)-1,4,7,10-tetraazacyclododecane (11) and 1 reacts with 4-benzyl-diethylenetriamine (4) and Cu(O2CCH3)2 forming the dimeric copper complex [{C6H5CH2N(CH2CH2NH2}2Cu(μ-Cl)OSO2CH3]2 (12). The 1H and 13C NMR spectra of the new compounds as well as the single crystal X-ray structure analyses of 9a, 11, and 12 are reported and discussed.
Metal Complexes of Biologically Important Ligands, CLVI [1]. Metal Complexes of 4-Iodo-L-phenylalanine. Oxidative Addition of 4-Iodo-L-phenylalanine Ester to Palladium(0)
Authors: Kayser Bernd , Beck Wolfgang
Published: August 2018

4-Iodo-L-phenylalanine gives with the chloro bridged compounds [(Et3P)PtCl2]2, [(Et3P)PdCl2]2 and [Cp*IrCl2]2 the N,O-chelate complexes (L)(Cl)M[NH2-C(H)(CH2C6H4I)CO2] (M = Pt, Pd, Ir; L = PEt3, Cp* ) (1 - 3). Oxidative addition of N-protected 4-iodo-L-phenylalanine methylester to Pd(dba)2 in the presence of 2,2’-bipyridyl or of triphenylphosphine affords the p-phenyl metallated amino acids (bipy)(I)Pd[C6H4CH2C(H)(NHR)CO2Me] (4,5) and (PPh3)2 (I)Pd[C6H4CH2C(H)(NHR) CO2Me] (6,7). Oxidative addition of the coordinated 4-iodo-Lphenylalaninate in (Et3P)(Cl)M[NH2C(H)(CH2C6H4I)CO2] to Pd(dba)2 was also observed.
A Novel Crown-Ether Stabilized Oxonium Halogenochalcogenate(IV): [H7O3(Bis-dibromo-dibenzo-30-crown-10)][Se2Br9]·1.5CH2Cl2
Authors: Hammerschmidt Adrienne , Beckmann Illenora , Läge Mechtild , Krebs Bernt
Published: August 2018

The title compound [H7O3(bis-dibromo-dibenzo-30-crown-10)][Se2Br9] ·1.5CH2Cl2 (1) was isolated from a solution of SeBr4 and dibenzo-30-crown-10 in CH3CN/CH2Cl2 containing a small amount of hydrobromic acid. During the reaction the crown ether is brominated by HBr. The compound crystallizes in the monoclinic space group P21/n with a = 17.688(11), b = 14.921(6), c = 20.521(12) Å , β = 97.71(5)°, and Z = 4. 1 is a novel example in the series of supramolecular halogenochalcogeno acids prepared in our group in which different oxonium cations are stabilized and encapsulated by crown ethers. Especially in this class of superacids complexation by cyclic polyethers offers covenient and variable possibilities for the controlled synthesis of oxonium cations. In the present case the large dibenzo-30-crown-10 ring systems are able to stabilize trinuclear [H7O3]+ cations within their cavities. Besides the macromolecular cations and some dichloromethane solvent molecules, the crystal structure of 1 contains molecular [Se2Br9]− ions with approximate D3h symmetry, each consisting of two face-sharing SeBr6 octahedra.
Formamidinium Salts of Low Valent Metal Halide Anions MX3 – (M = Ge, Sn) and M2X6
2– (M = Ga, In)
Authors: Tian Xin , Pape Tania , Mitzel Norbert W.
Published: August 2018

Tetramethylformamidinium trichlorogermanite, [CH(NMe2)2][GeCl3], tetramethylformamidinium trichlorostannite, [CH(NMe2)2][SnCl3], bis-(tetramethylformamidinium hexaiododigallate, [CH(NMe2)2]2[Ga2I6] and bis-(tetramethylformamidinium hexachlorodiindate, [CH(NMe2)2]2[In2Cl6] have been prepared by the reactions between tetramethylformamidinium chloride, [CH(NMe2)2]Cl, and the corresponding low valent halides GeCl2 (as dioxane adduct), SnCl2, “GaI” and InCl. Their crystal structures have been determined by single crystal X-ray diffraction. [CH(NMe2)2][GeCl3] aggregates in a centrosymmetric dimeric structure, in which two trigonal pyramidal GeCl3 units are connected together by two weak Ge···Cl bonds and each Ge atom is bonded to one cation by a weak Ge···N contact. Two sets of weak hydrogen bonds C-H···Cl are observed with bond lengths of 2.87(2) Å and 2.85(2) Å . In [CH(NMe2)2][SnCl3], the SnCl3 − units adopts a (3+3) coordination with three normal Sn-Cl bonds and three weak Sn···Cl contacts. [CH(NMe2)2]2[Ga2I6] and [CH(NMe2)2]2[In2Cl6] contain metal-metal bonded anions with distorted staggered ethane-like conformations. The metal-metal bond lengths are 2.423(1) Å (Ga-Ga) and 2.719(1) Å (In-In). Their Raman spectra contain intense bands at 118.7 cm−1(Ga-Ga) and 174.7 cm−1(In-In) associated with metal-metal stretching modes.
Organoaluminium and -gallium Lewis-Acid Adducts of Tetramethylmethylenediamine
Authors: Mitzel Norbert W. , Lustig Christian
Published: August 2018

The compounds Me3Al-Me2NCH2NMe2-AlMe3 (1) and Me3Ga-Me2NCH2NMe2-GaMe3 (2) were prepared by reacting Me2NCH2NMe2 (TMMDA) with two equivalents of the metal trialkyls in hydrocarbon solutions.With the ether adduct Me3Ga·OEt2 Me2NCH2NMe2 reacts to give the monoadduct Me2NCH2NMe2-GaMe3 (3). These compounds were characterized by NMR spectroscopy (1H, 13C and 27Al) and by elemental analyses. Crystal structure investigations show 1 and 2 to be monomeric and to a adopt a trans,trans-conformation for their M-N-C-N-M backbones. 3 is also monomeric in the solid state, but adopts a cis,trans-conformation. Tetramethylformamidinium chloride and also chlorotetramethylformamidinium chloride reacts with lithium aluminium hydride to give the mono-adduct [Me2NCH2NMe2-AlH3]2 (4), which is dimeric and can be regarded as a double TMMDA adduct to Al2H6 with five-coordinate Al atoms. Ab initio calculations on the MP2/6- 311G** level of theory have been performed for the model compound H3N-H2Al(μ-H)2AlH2-NH3 to obtain its molecular structure and vibrational spectrum for comparison with 4 and for the assignment of its vibrational spectrum.
Synthesis and Reactivity of Ti(III) Tris(tert-butoxy)siloxy Complexes
Authors: Lugmair Claus G. , Tilley T. Don
Published: August 2018

Reaction of TiCl3(THF)3 with 3 equivalents of LiOSi(OtBu)3 produces the Ti(III) siloxide Ti[OSi(OtBu)3]3(THF)2 (1), and a 1:4 ratio of the same reagents gives {LiTi[OSi(OtBu)3]4}x. Upon heating to 95 °C, compound 1 converts via THF ring-opening to [(tBuO)3 SiO]3TiO(CH2)4Ti[OSi(OtBu)3]3. The pyridine adduct Ti[OSi(OtBu)3]3(pyr)2, and polymeric {Ti[OSi(OtBu)3]3(4,4’-bipyridine)}n, are also described. Electronic spectra for the Ti[OSi (OtBu)3]3L2 complexes indicate D3h symmetry, and similar results for the 4,4’-bipyridine adduct suggest a linear polymeric structure.
Zwischenmolekulare Wechselwirkungen in den Kristallstrukturen von 4-Halogenbenzolsulfonamiden (Halogen = Fluor, Chlor, Brom, Iod) und 4-Methylbenzolsulfonamid / Intermolecular Interactions in the Crystal Structures of 4-Halobenzenesulfonamides (Halogen = Fluorine, Chlorine, Bromine, Iodine) and 4-Methylbenzenesulfonamide
Authors: Zerbe Eva-Maria , Moers Oliver , Jones Peter G. , Blaschette Armand
Published: August 2018

Low-temperature single-crystal X-ray structures of the following 4-X-benzenesulfonamides have been studied in order to compare the effects of the 4-substituents on the molecular packings: X = F (1, orthorhombic, Pbca, Z′ = 1, structure previously reported), X = Cl (2, monoclinic, P21/n, Z′ = 1), X = Br (3, isostructural with 2), X = Me (4, isomorphous with 2 and 3, room-temperature structure previously reported, accurate redetermination in this work), X = I (5, monoclinic, Pc, Z′ = 2 molecules with markedly different conformations). As a common feature, the five structures display molecular layers comprising an internal polar lamella of H2NSO2 groups engaged in N-H···O hydrogen bonding, and hydrophobic peripheral regions consisting of the 4-X-substituted phenyl rings. Whereas each molecule in 1 - 4 is linked to four adjacent congeners by ordinary two-centre hydrogen bonds, the sterically demanding iodo substituent in 5 causes all N-H···O interactions to split up into longer N-H(···O)2 three-centre bonds that are used to connect each molecule to six adjacent molecules. Important packing differences between 1 and the other structures appear to emanate from the high electronegativity of fluorine. In 2- 5, the polar lamellae are approximately planar, and the aromatic groups protrude obliquely (2 - 4) or vertically (5) from the lamellae to form translationgenerated parallel stacks separated by broad voids. Contiguous layers are packed via stack-void interlocking, thus creating high packing density and, concomitantly for 2, 3 and 5, interlayer halogen bonds of the type Cl···O, Br···O or I···N, respectively; none of the four structures exhibits π···π stacking interactions between aromatic rings or short halogen-halogen contacts. This simple packing architecture does not hold in the case of 1. Here, the polar lamella adopts a zigzag profile with acute angles of ca. 60°, allowing high packing density to be achieved by intralayer π···π stacking between parallel rows of geometrically convergent aryl rings. The electronegative fluorine atoms, efficiently shielded from the polar lamellae, are segregated into the regions between adjacent layers and form short F···F interlayer contacts about crystallographic centres of inversion.
Packungsdichte und Wertigkeit von Lithium und Natrium unter Druck / Packing Density and Valence of Lithium and Sodium under Pressure
Authors: Trömel Martin , Taxer Karlheinz
Published: August 2018

The volume changes of lithium and sodium under pressure are discussed with respect to the packing density of the atoms and their valence. In densely packed Li I (bcc), Li II (fcc), and Li III (α-Hg type), valence increases from 1 at ≈ 5 GPa to ≈ 2.5 at 40 GPa. The maximum valence 3 is attained in Li IV (body-centered cubic, 16 atoms per cell, packing density q = 0.965) at 47 GPa. In densely packed Na I (bcc) a linear increase of valence from 1 at ≈ 10 GPa to 2.9 at 65 GPa is found which continues in Na II (fcc) up to 4.1 at 103 GPa.
A Gallium-Nitrogen Heteronorbornane With Bulky Tbutyl Substituents
Authors: Tiana Xin , Fröhlich Roland , Mitzela Norbert W.
Published: August 2018

Selective formation of 3,3,6,6-tetra-tbutyl-1,4-dimethyl-3,6-digallium-1,4-diaza-norborane is achieved by the reaction of bis(lithiomethyl-methylamino)methane with ditbutylgallium chloride by simultaneous formation of two dative metal-carbon and two metal-nitrogen bonds accompanied by two ring closures. Despite the high steric demand of the tbutyl groups, the norbornane-like structure is favoured over potential isomers containing three-membered rings and over polymeric aggregation. The compound was identified by elemental analysis, NMR spectroscopy (1H, 13C) and by determination of its crystal structure in which it is present as a monomer
Struktur des Addukts von Trimethylzinnchlorid Me3SnCl mit Trimethylzinnhydroxid Me3SnOH / Structure of the Adduct of Trimethyltin Chloride Me3SnCl with Trimethyltin Hydroxide Me3SnOH
Authors: Lerner Hans-Wolfram , Ilkhechi Alireza Haghiri , Bolte Michael , Wagner Matthias
Published: August 2018

Benzene solutions of Me3SnCl when exposed to moisture yield the adduct Me3SnCl·Me3SnOH·H2O. This adduct represents an intermediate in Me3SnCl hydrolysis. The structure of Me3SnCl·Me3SnOH·H2O features an array of Me3Sn units connected alternatingly by bridging Cl and OH ligands
Spectroscopic, Magnetic and Crystal Structure Analysis of Diammine-bis(2,6-dibromo-4-chlorophenolato-O)copper(II)
Authors: Gökağaç Gülsün , Yildirim Leyla Tatar , Sonsuz Muammer , Şen Fatih
Published: August 2018

The [Cu(C6H2Br2ClO)2(NH3)2] complex was synthesized and characterized by XRD, UV/vis, FTIR, DSC, elemental analysis and magnetic susceptibility measurements. The structural analysis of the title complex indicated that it is a monomeric centrosymmetric compound which crystallizes in the monoclinic system, P21/c, and has a trans-planar CuO2N2 coordination [Cu-O 1.940(5) and Cu-N 1.978(7) Å ]. In the coordination sphere of the Cu atom, there are long range interactions with Br2 and the centrosymetrically related Br2i (i: −x,−y,−z) atoms [Cu-Br2: 3.079(2) Å ], resulting in a tetragonally elongated octahedral structure for the CuO2N2Br2 coordination. The molecules form one-dimensional chains along the x-axis of the unit cell held together by intermolecular hydrogen bonds.
An Unusual Nitrogenous Terphenyl Derivative from Fruiting Bodies of the Basidiomycete Sarcodon scabrosus
Authors: Ma Bing-Ji , Liu Ji-Kai
Published: August 2018

A new nitrogenous metabolite with p-terphenyl core, sarcodonin δ (1), together with two known p-terphenyl metabolites (7, 8), was isolated from the fruiting bodies of the basidiomycete Sarcodon scabrosus. The structures of these compounds were elucidated by spectral and chemical methods.
1,1-Ethylboration of Alkyn-1-yl- (dichloro)silanes: Alkenes Bearing Dichlorosilyl and Diethylboryl Groups
Authors: Wrackmeyer Bernd , Shahid Khadija , Ali Saqib
Published: August 2018

The 1,1-ethylboration of dichloro(hexyn-1-yl)silane, Cl2 Si(H)-C≡C-Bu, affords selectively an alkene which is the first example with dialkylboryl and dichlorosilyl groups in cis-positions at the C=C bond. The analogous reaction of dichloro( trimethylsilylethynyl)silane, Cl2(H)Si-C≡C-Si Me3, leads to a 4:1 mixture of alkenes, in one of which the boryl and dichlorosilyl groups are in trans-positions. The alkenes were characterized by a consistent set of NMR data.
Synthesis and Reactivity of Boron-Functionalized C2B5-closo-Carboranes
Authors: Nie Yong , Goswami Avijit , Siebert Walter
Published: August 2018

Treatment of the nido-2,3-Et2C2B4H4
2−dianion (1) with monoboron reagents led to closo-C2B5 carborane derivatives with functional substituents at the inserted apical boron atom. The reactions of 1 with BX3 (X = Br, I) afforded the corresponding closo-1-X-2,3-Et2C2B5H4 (2a,b), and with PhCΞCBcat (cat = O2C6H4) produced the alkynyl-substituted closo-1-CΞCPh-2,3-Et2C2B5H4 (2c). Pd-catalyzed Negishi-type cross-coupling reactions of 2b with RCΞCZnCl at room temperature gave the corresponding closo-1-CΞCR-2,3-Et2C2B5H4 derivatives 2d-f, R = SiMe3, Me, and tBu, respectively. Compound 3 with two C2B5 moieties linked via a C=C unit was obtained by a similar boron incorporation reaction with cis-Cl2B5(Et)C=C(Et)BCl2. The reactions of 2c,d with Co2(CO)8 afforded the dicobaltatetrahedrane-substituted carboranes 4c and d, in which the clusters C2B5 and Co2C2 are connected by a B-C bond. Compounds 4c,d lost the apical boron on wet silica gel or sand to give the nido-C2B4-C2Co2 compounds 5c,d. Formation of the carboranyl-substituted (η5- C5H5)Co(cyclobutadiene) complex 6c was observed in the reaction of 2c with (η5-C5H5)Co(C2H4)2. The composition of the products follows from NMR and MS data.
Synthesis of Pyridine-Thioethers via Mono- and Tricationic Pyridinium Salts
Authors: Schmidt Andreas , Mordhorst Thorsten
Published: August 2018

On nucleophilic substitution with S-nucleophiles at room temperature, 1-(4-dimethylamino)- [2,3,5,6-tetrachloropyridin-4-yl]pyridinium chloride (2) yielded tetrachloro-4-sulfanylpyridines and 2,3,5-trichloro-4,6-disulfanylpyridines depending on the reaction conditions. Similarly, the tricationic (3,5-dichloropyridine-2,4,6-triyl)-1,1’,1”-tris[4-(dimethylamino)pyridinium] trichloride 3 was reacted with S-nucleophiles to give the corresponding 3,5-trichloro-2,4,6-trisulfanylpyridines under mild conditions.
Hydroxylamin-Funktion als Nachbargruppe bei Dehydrierungen / Hydroxylamine Function as Neighboring Group with Dehydrogenations
Authors: M¨ohrle Hans , Arndt Petra
Published: August 2018

The β -amino-hydroxylamines 5a - d are prepared of the α-amino-oximes 1a - d with boranedimethylsulfide. With mercury-EDTA, 5a - d react to (E/Z)-oxime-lactams 3a - d and benzaldoxime 7. Additionally 5b,c give the bicyclic amidine-N-oxides 8b,c, which slowly hydrolyze to the hydroxylamine-lactams 9b,c. These are easily oxidized to (E/Z)-3b,c. Postulated as intermediates in the mercury-assisted reduction of 5, the cyclic hydroxylamines 10a - d are available from the nitrones 4a - d with LiAlH4. From 10a - d with mercury-EDTA the same products are obtained as from 5a - d but without 7. Only the pyrrolidine 10a forms besides (E/Z)-3a the nitrone 4a. Thinlayer chromatography shows that the pure isomers of 3a - d in solution isomerize, contrary to the amine-oximes 1a - d. The configuration of the oxime-lactams depends on the manner of preparation. With mercury-EDTA, 1b,c yield 3b,c with retention of the configuration, while the oximation of phenacyl-lactams 13b,c give rise to (E/Z)-mixtures of 3b,c. The condensed imidazoles 12 result from the nitrones 4a - d and the dihydrooxadiazines 2a,d on treatment with hydrogen chloride.
Lithium Bis(triisopropylsilyl)phosphanide and its Pentacarbonyltungsten Adduct: Synthesis and Crystal Structures of the Dimer [(thf)Li-P(SiiPr3)2]2 and the Solvent-Separated Ion Pair [(thf)4Li]+ [(OC)5W-P(SiiPr3)2]–
Authors: Westerhausen Matthias , Rotter Thomas , Görls Helmar , Birg Christin , Warchhold Marcus , Nöth Heinrich
Published: August 2018

The lithiation of bis(triisopropylsilyl)phosphane with n-butyllithium in THF gave quantitatively dimeric (thf)LiP(SiiPr3)2 (1) with three-coordinate lithium atoms. The molecular structure of 1 shows Li-P bond lengths of 253.3(6) pm. In order to obtain the pentacarbonyltungsten complex of the sterically demanding phosphanide, (thf)W(CO)5 was reacted with (thf)LiP(SiiPr3)2 in THF. The resulting solvent-separated complex [(thf)4Li]+ [(OC)5WP(SiiPr3)2]− (2) was structurally characterized and shows a very large W-P distance of 266.65(7) pm.
Preparation, Crystal Structure, Properties, and Electronic Band Structure of TlTaSe3
Authors: Teske Christoph L. , Bensch Wolfgang , Benea Diana , Minár Jan , Perlov Alexander , Ebert Hubert
Published: August 2018

TlTaSe3 was prepared from a fused mixture of Tl4Ta2Se11, Ta and Se in the molar ratio 1:2:1. The compound shows dimorphism with H-TlTaSe3, hexagonal, space group P63/mmc, a = 7.2436(6), c = 5.9736(6) Å , c/a = 1.213 and O-TlTaSe3, orthorhombic, space group Pnma, a = 9.554(13), b = 3.6244(6), c=14.7271(17) Å . The crystal structure of H-TlTaSe3 is isotypic to BaVSe3 whereas that of O-TlTaSe3 is closely related to the NH4CdCl3-type. Characteristic features of the structures are: 1
∞[TaSe3
2−] chains of regular octahedra sharing faces along [001] for the hexagonal form and columns of double edge-sharing octahedra 1
∞[Ta2Se6
2−] running along [010] for O-TlTaSe3. The columns are each separated by Tl+ ions with the coordination number CN = 12 and CN = 8 respectively. The structures are compared and discussed in context with other isotypic structures of chalcogenides. The orthorhombic modification O-TlTaSe3 is a semiconductor while H-TlTaSe3 shows conventional metallic behaviour. The electronic structures of both modifications are discussed on the base of band structure calculations performed within the framework of density functional theory.
Münzmetall-Lanthanid-Chalkogenide: I. Kupfer(I)-Lanthanid(III)-Sulfide der Zusammensetzung CuMS2 (M = La – Nd, Sm, Gd, Tb) im monoklinen A-Typ / Coinage Metal Lanthanide Chalcogenides: I. Copper(I) Lanthanide(III) Sulfides of the Composition CuMS2 (M = La – Nd, Sm, Gd, Tb) with the Monoclinic A-Type Structure
Authors: Strobel Sabine , Lauxmann Petra , Schleid Thomas
Published: August 2018

Single crystals of the ternary copper(I) lanthanide(III) sulfides with the composition CuMS2 (M = La - Nd, Sm, Gd, Tb) form within seven days at 800 °C by oxidation of elemental copper and lanthanide metal with sulfur (molar ratio: 1 : 1 : 2) in evacuated silica tubes when equimolar quantitites of CsCl are present as flux. The crystal structures (monoclinic, P21/c, Z = 4; e. g. CuLaS2: a = 662.04(6), b = 730.89(6), c = 692.73(6) pm, β = 98.741(7)° and CuTbS2: a = 639.13(6), b = 700.02(6), c = 670.46(6) pm, β = 98.214(7)°) exhibit corrugated layers 2
∞ {[Cu(S1)3/3(S2)1/1]3−} parallel to (100) which consist of vertex-linked pairs of [CuS4]7− tetrahedra sharing a common edge ([Cu2S6]10−). Their three-dimensional cross-linkage is achieved by M3+ cations in monocapped trigonal prismatic coordination of seven S2− anions. The metal sulfur distances in the [CuS4]7− units cover with 230 - 233 (Cu-S2) and 231 - 238 (Cu-S1) as well as 241 - 248 (Cu-S1’) and 245 - 251 pm (Cu-S1”) a rather broad range, whereas those within the [MS7]11− polyhedra lie relatively closer together (M-S: 276 - 307 pm). The present work is the first comprehensive account of the knowledge acquired from X-ray single-crystal diffraction data for the whole isotypic series CuMS2 (M = La - Nd, Sm, Gd, Tb).
Derivate der 1,3-Dimethyl-5-methylen-barbitursüure / Derivatives of 1,3-Dimethyl-5-methylenebarbituric Acid
Authors: Kuhn Norbert , Kuhn Alois , Niquet Elke , Steimann Manfred , Sweidan Kamal
Published: August 2018

1,3-Dimethylbarbituric acid (1, R = Me) reacts with aqueous formaldehyde in the presence of pyridine to give 1,3-dimethyl-2,4,6-trioxo-5-pyridinomethyl-1,3-perhydrodiazin-5-ylpyridinium ylide (6) in good yield. From 6 and 2,3-dihydro-1,3-diisopropyl-4,5-dimethylimidazol- 2-ylidene (7), the zwitterionic imidazolium derivative 1,3-dimethyl-2,4,6-trioxo-5-(1,3-diisopropyl- 4,5-dimethylimidazoliomethyl)-1,3-perhydrodiazin-5-yl-imidazolium ylide (8) is obtained. Similarly, the phosphonium compound 1,3-dimethyl-2,4,6-trioxo-5-triphenylphosphoniomethyl-1,3- perhydrodiazin-5-y l-phosphonium ylide (9) is obtained from 6 and PPh3. The crystal structures of 8 and 9 are reported.
Synthesis and Structural Characterization of N-[4-(2-Hydroxyethyl)-1,2,4-oxathiazinan-3-ylidene]-benzamide and its Mercury(II) Chloride Adduct
Authors: Angulo-Cornejo Jorge R. , Ayala-León Ketty , Herbosa Gabriel García , Cuevas José V. , Diez Virginia , Richter Rainer , Hennig Lothar , Beyer Lothar
Published: August 2018

The synthesis of N-[4-(2-hydroxyethyl)-1,2,4-oxathiazinan-3-ylidene]-benzamide (2a) and N-[4- (2-hydroxyethyl)-1,2,4-oxathiazinan-3-ylidene]-2-fluorobenzamide (2b) by oxidation of the corresponding 1,1-bis(2-hydroxyethyl)-3-aroylthioureas with potassium iodate in aqueous solution is reported. Variable temperature 1H NMR spectra of 2a prove that the heterocyclic 1,2,4-(O, S,N) sixmembered ring is involved in a dynamic chair-boat conformational interconversion. Molecular mechanic calculations show that the chair conformation is more stable than the boat conformation by 3.0 kcal/mol. The synthesis of the adduct [(2a)·0.5 HgCl2] 3 as well as the X-ray structural characterization of 2a and 3 are also reported.
Syntheses and Characterization of Two New 4,4’-Bithiazole d10 Complexes, Structural Characterization of M(DABTZ)2(CH3COO)](ClO4) · 2H2O (M = Zn, Cd)
Authors: Abedini Jafar , Morsali Ali
Published: August 2018

New zinc(II) and cadmium(II) complexes of the 2,2’-diamino-4,4’-bithiazole (DABTZ) ligand, [M(DABTZ)2(CH3COO)](ClO4), have been synthesized and characterized by elemental analysis, IR, 1H NMR and 13C NMR spectroscopy. The structural characterization of the Cd(DABTZ)2(CH3COO)](ClO4) · 2H2O complex shows the complex to be a monomer and the Cd atom to be coordinated by four nitrogen atoms of the “DABTZ” ligands and two oxygen atoms of the acetate anion. There is an edge-to-edge π-π stacking interaction between the parallel aromatic rings.
Synthesis, Characterisation, Structure, and Magnetic Properties of [Ni{H2NCH(CH3)CH2NH2}3][Fe(CN)5NO]·H2O
Authors: Saha Manas Kumar , Dey Dilip Kumar , Samanta Brajagopal , Dey Subrata Kumar , Malik K. M. Abdul , Mitra Samiran
Published: August 2018

The complex [Ni(pn)3][Fe(CN)5NO]·H2O (1) was synthesised by the reaction of [Ni(pn)3]Cl2 (pn = racemic propane-1,2-diamine) with Na2[Fe(CN)5NO]·2H2O in aqueous solution and has been charaterised by IR and Mössbauer spectroscopy and magnetic studies. Single crystal structure analysis revealed octahedrally coordinate cations [Ni(pn)3]2+ and anions [Fe(CN)5NO]2−.