bluuebunny/crossref_metadata_2025 huggingface dataset:
Darstellung, Kristallstruktur, Schwingungsspektren und Normalkoordinatenanalyse von [Os(acac)3]/ Synthesis, Crystal Structure, Vibrational Spectra, and Normal Coordinate Analysis of [Os(acac)3]
Authors: Dallmann K. , Preetz W.
Published: February 2015

In the reaction of K2[OsCl6] with boiling water/acetylacetone (1:1) a mixture of different chloro-acetylacetonato complexes is formed, from which [Os(acac)3] can be isolated by column chromatography with dichloromethane on silica gel. The crystal structure of [Os(acac)3] (mo­noclinic, space group P21/c,a = 13.968(5), b = 7.517(5), c = 16.455(5) Å ,β = 98.939(5)°, Z = 4) has been determined by single crystal X-ray diffraction analysis. High resolution IR and Raman spectra were measured at low temperature (10K). Based on the molecular parameters of the X-ray structure determination a normal coordinate analysis has been performed and the normal modes of vibration have been assigned. With a set of 32 force constants, taking into account the intraligand vibrations, a good agreement between observed and calculated frequencies has been achieved. The valence force constants are fd(OsO) = 3.19 and fd(OC) = 6.74 mdyn/Å.
Synthese und Kristallstruktur von [H2NMe2]+[(Me2NH)2 TiCl4]-/Synthesis and Crystal Structure of [H2NMe2]+[(Me2NH)2TiCl4]-
Authors: Bettenhausen Regina , Milius Wolfgang , Schnick Wolfgang
Published: February 2015

The title compound has been synthesized as a green solid by the reaction of MeCl2 SiNHSiMe3 and Ti(NMe2)4 in CH2Cl2. The crystal structure was determined by single crystal X-ray methods at room temperature (C2/c, a = 1825,7(4), b = 909,9(2), c = 1116,1(2) pm, β = 125,09(3)°, Z = 4,R1= 0,047, wR2 = 0,147) to be an ionic salt [H2NMe2]+[(Me2NH)2TiCl4]- . The central titanium(III) atom of the anion is bound to four Cl atoms and weakly coordinated by two Me2NH ligands.
Enantioselective Catalysis, XVII [1]. Enantioselective Catalytic Hydrogenation of Unfunctionalized Ketones
Authors: Nagel Ulrich , Roller Christoph
Published: February 2015

Three diastereomeric rhodium bisphosphane complexes have been applied to asymmetric hydrogenation of unfunctionalized, non-chelating aliphatic and aromatic ketones. The ee values of the catalysis products differ considerably for the diastereomerical catalysts. 70% ee were obtained in hydrogenating butyrophenone, and 83.7% ee for pinacoline. The results depend strongly on the solvent used.
Zur Kristallchemie der Silber-Mangan-Oxovanadate Ag2BaMnV2O8 und (AgCa2)Mn2(VO4)3 / On the Crystal Chemistry of the Silver Manganese Oxovanadates Ag2BaMnV2O8 and (AgCa2)Mn2(VO4)3
Authors: Rettich R. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of Ag2BaMnV2O8 (I) and (AgCa2)Mn2(VO4)3 (II) have been prepared by reactions of metallic silver and mixtures of MnCO3H2O , V2O5 and L/II; BaCO3/CaCO3. Crystal structure investigations by X-ray methods led to I: trigonal symmetry, C1
3i-P3̅, a = 5.5693(4), c = 7.2706(6) A, Z = 1 and II: cubic symmetry, O10
h-Ia3̅d, a = 12.6084(9) Å, Z = 8 . Despite of different symmetry compound I is strongly related to the monoclinic compounds Ag2SrCuV2O8 and Na2BaCuV2O8, respectively. II belongs to the garnets. Compound I is characterized by [BaOg] nets with incorporated V5+ and Ag+ ions. The [BaOg] nets are connected by Mn2+ ions. A discussion of structural details of I with respect to Ag2SrMnV2O8, Na2BaCuV2O8 and the two modifications of K3Na(CrO4 )2 is given.
Zur Synthese fluororganischer O-(Trimethylsilyl)-cyanhydrine / Synthesis of Fluoroorganic O-(Trimethylsilyl)Cyanhydrines
Authors: Sander Michael , Sundermeyer Wolfgang
Published: February 2015

Fluororganic and/or sterically hindered cyanohydrines are useful synthetic reagents, not readily available directly from e.g. aldehydes or ketones and hydrogen cyanide. By using trimethylsilyl cyanide (TMSCN), the obtained O-Silyl-cyanohydrines can be applied successfully for the same purpose. Selected examples of the type R1R2C-CN(OSiMe3) 1 -12 are presented which prove the extensive applicability of this reaction [R = (fluoro)alkyl, (fluoro)aryl, anthryl, cyclopropyl, CCl3, CBr3 etc.]. Malodinitrile derivatives RC(CN)2OSiMe3 14 were obtained from carboxylic acid chlorides, α-, β- and 7 -Diketones react with formation of the corresponding linear or cyclic doubly substituted O-Silylcyanohydrines 16, 17, 21, 22. The enol-form of hexafluoroacetylacetone reacts with silylation to give the E-isomer of the silylenol ether 18, the carbonyl group of which forms the O-Silylcyanohydrine 19. With Me2Si(CN)2 both reaction steps occur intramolecular, yielding a 2,6-dioxa-l-sila-3-cyclohexene 20.
Supersilylverbindungen Der Borgruppenelemente, IV [1]. Supersilylelementhalogenide tBu3SIEX2 Und (tBu3Si)2Ex Mit E = Al, Ga, In: Synthesen, Eigenschaften, Strukturen [2] / Supersilylated Compounds of the Thirteenth Group, IV [I]. Supersilylelement Halides tBu3SIEX2 And (tBu3Si)2Ex with E = Al, Ga, In: Syntheses, Properties, Structures [2]
Authors: Wiberg Nils , Amelunxen Kerstin , Lemer Hans-Wolfram , Nöth Heinrich , Knizek Jörg , Krossing Ingo
Published: February 2015

Water and oxygen sensitive compounds (tBu3SiEX2)2, tBu3SiEX2 Do and (tBu3Si)2EX (E = AI, Ga, In; X = (F), Cl, Br; Do = OR2, NR3) have been synthezised by reaction of EX3 with tBu3SiNa in the absence or presence of donors. In addition, (tBu3Si)AlBr2, (tBu3Si)2InF and tBu3SiInBr2 were prepared by reaction of AlBr3 with (tBu3Sij2Zn or of (tBu3Si)2In- In(Si/Bu3)2 with AgF2 and HBr, respectively. The adduct [tBu3SiAlBr2 · AlBr3 ·1/2MgBr2]2 is formed from AlBr3 and (tBu3Si)2Mg(THF)2. Thermal decomposition of the compounds in solution or in the gas phase leads to the formation of tBu3SiEX2 (from the dimers or the donor adducts) and of tBu3SiX. The Lewis acidity of tBu3SiEX2 against donors increases in the direction Do = Et2O < THF < NEtMe2. Dehalogenation of (tBu3Si)2ECl with tBu3SiNa(THF)2 in pentane at room temperature leads to clusters (tBu3Si)4Al2, (tBu3Si)3Ga2
•, (tBu3Si)4In2 and (tBu3Si)3Ga2Na(THF)3, reduction of tBu3SiGaCl2 with Na or K in heptane at 100°C to the tetrahedran (tBu3Si)4Ga4. The structures of (tBu3SiGaCl2)2, (tBu3Si)2GaCl, and [tBu3SiAlBr2 AlBr3 ·1/2MgBr2]2 have been determined by X-ray structure analysis.
Untersuchungen zum chemischen Transport von YX3 mit AlX3 und zur Existenz von gasförmigen und festen Komplexen YAl3 X12 (X = Br, I) / Investigations on the Chemical Transport Reaction of YX3 with AlX3 and on the Existence of Gaseous and Solid Complexes YAl3 X12 (X = Br, I) H
Authors: Oppermann H. , Herrera S. , Huong Dao Quoc
Published: February 2015

The dominant gaseous complexes YAl3Br12 and YAl3I12 were generated in the chemical trans­port reactions of YBr3 with AlBr3 and YI3 with AlI3. The enthalpy of formation

ΔH0
B(YAl3Br12,g,298) = -484,5 ± 6 kcal/mol

and the standard entropy

S°(YA13B12,g,298) = 290,0 ± 7,5 cal/K·mol

have been calculated. It follows from total pressure measurements of mixtures of YBr3,s with AlBr3,1 and YI3,s with AlI3,1 respectively, that complexes YAl3Br12,s and YAl3I12,s do not exist up to the boiling points of the aluminium trihalides.
Synthesis and Mesomorphic Properties of Polymethylene-α,ω–bis [2-thio- 5-(4',4"n-alcoxybenzoyIoxy)phenyl]-1,3,4-oxadiazole
Authors: Aguilera C. , Parra M. , Fuentes G.
Published: February 2015

Three homologous series of polymethylene-α,ω-bis[2-thio-5(4′,4″n-alkoxybenzoyloxy)- phenyl]-1,3,4-oxadiazole (series 5 a, b, c), are reported.The compounds have identical mesogenic units at both ends of a spacer (i.e. they are twins). These twins possess a spacer of 6, 8 and 10 carbon atoms joined directly to the oxadiazole ring through sulphur atoms. The lateral alkylic chains vary between 6 and 10 carbon atoms.The presence of enantiotropic and monotropic nematic phase is related to the length of the spacer group. The influence of molecular structure on the mesomorphic properties has been studied. Mesomorphic properties and phase transitions have been determined using polarizing hot-stage microscopy and differential scanning calorimetry.
Syntheses and Structures of Cyclopentadienyl Arsenic (III) Compounds Part IIIa: Tetraisopropylcyclopentadienyl Arsenic (III) Dibromide and Tetraisopropyl- cyclopentadienyl Arsenic (III) Diiodide (TipCpAsBr2, TipCpAsI2)
Authors: Megges Klaus , Avtomonov Evgeni V. , Becker Ralf , Lorberth Jörg
Published: February 2015

1,2,3,4-Tetraisopropylcyclopenta-2,4-dien-1-yl arsenic (III) dihalides, viz. TipCpAsX2 (1 X = Br, 2 X = I), have been prepared by direct metathesis reaction between the corresponding arsenic (III) trihalides with one equivalent of TipCpK at low temperature in good yields. Alternatively, 2 has been prepared via halogen exchange reaction between TipCpAsCl2 (3) and KI. New compounds have been characterised by spectroscopic m ethods ( 1H, 13C NMR. EI-MS) and elemental analyses. The crystal structures of 1 and 2 have been determined by X-ray diffraction methods. The AsX2-moiety in 1 and 2 occupies an allylic position neighbouring to an isopropyl substituent. The arsenic fragment is o-bound to the cyclopentadienyl ligand, indicating remarkable π-interactions with the diene part of the cyclopentadienyl ring.
Die Tieftemperaturkristallstruktur von Trimethylsilanol / The Low Temperature Crystal Structure of Trimethylsilanol
Authors: Minkwitz Rolf , Schneider Stefan
Published: February 2015

A preparation of trimethylsilanol by hydrolysis of bis(trimethylsilyl)carbonate in diethylether at -20°C is reported. At -80°C, the crystals are monoclinic, space group P21/c, Z = 12 with cell dimensions a = 996.0(2) pm, b = 1730.2(3) pm, c = 1122.9(2) pm, β= 96,61(3)°. There are three independent Me3SiOH units with a slightly distorted tetrahedral C3SiO core structure.
An Aluminium-Oxide-Isopropoxide Cluster with Peripheral Ammonia Ligands
Authors: Tripathi Upendra M , Schier Annette , Schmidbaur Hubert
Published: February 2015

The reaction of toluene solutions of aluminium isopropoxide with ammonia gas, without exclusion of moisture, affords high yields of a decanuclear aluminium-oxide-isopropoxide-ammonia cluster of the composition [Al10O6(OiPr)18(NH3)8]. The compact centrosymmetric cluster units feature tetra-, penta- and hexa-coordinate aluminium atoms, tri- and tetra-coordinate interstitial oxygen atoms, and bridging and terminal isopropoxide groups. The ammonia molecules occupy peripheral positions at two types of aluminium atoms
CT Complexes Derived from Verdazyl Radicals
Authors: Nakatsuji Shin’ichi , Kitamura Akari , Takai Atsushi , Nishikawab Kazuyoshi , Morimoto Yukio , Yasuoka Noritaki , Kawamura Haruki , Anzai Hiroyuki
Published: February 2015

Several charge-transfer (CT) complexes derived from 1,5-diphenyl-3-(p-substituted-phenyl)- verdazyl radicals and TCNQF4 (2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane) or DDQ (2,3-dichloro-5,6-dicyano-1,4-benzoquinone) were prepared and their magnetic properties were investigated. The X-ray crystal structural analyses on the CT complexes consisted of 3-(4-methoxyphenyl)-, 3-(4-tolyl)- as well as 3-(4-chlorophenyl)-verdazyl radicals and TCNQF4 were carried out and correlated with their magnetic properties in which large decrease of magnetic susceptibility was observed in each complex.
Die Kristallstrukturen von MesSn(Cl)Me2 und Mes2SnCl2 / The Crystal Structures of MesSn(Cl)Me2 and Mes2SnCl2
Authors: Kräuter Thomas , Neumüller Bernhard
Published: February 2015

Single crystals of MesSn(Cl)Me2 (1) and Mes2SnCl2 (2) were obtained by the reactions of MesGaCl2 with Me3SnF and Mes3SnF, respectively. 1 and 2 are monomeric molecules in the solid state. 1: space group P21/n, Z = 4. lattice dimensions at -70°C: a = 1202,3(1), b = 739,1(1), c = 1441,3(1) pm , β = 102,71(1)°, R1 = 0,0469; 2: space group Pbcn, Z = 4, lattice dimensions at -50°C: a = 1107,0(2), b = 949,9(1), c = 1729,8(2) pm, R1= 0,049.
Reaktionen von Lithiumhydridosilylamiden mit Carbonylverbindungen und Gemischen von Carbonylverbindungen und Chlortrimethylsilan / Reactions of Lithium Hydridosilylamides with Carbonyl Compounds and Mixtures of Carbonyl Compounds and Chlorotrimethylsilane
Authors: Schneider Jan , Popowski Eckhard , Fuhrmann Hans
Published: February 2015

The lithium hydridosilylamides Me2(H)SiN(Li)R (1: R = CMe3, 2: R = SiMe3) were allowed to react either with the non-enolizable carbonyl compounds CH2=C(Me)CHO, PhCHO and Ph2CO followed by trapping with chlorotrimethylsilane (A), or with mixtures of these carbonyl compounds and chlorotrimethylsilane (B). In the second case the course of the reactions is determined by the carbonyl compound. The composition of the reaction mixtures is nearly the same according to A and B.

Main products in the reactions with the aldehydes are the corresponding imines R′CH=NR (R′ =CH2=C(Me), Ph) 3 , 4 , 8 ,9 formed by addition of the hydridosilylamides to the C = O group of the aldehydes and subsequent LiOSiMe2H elimination. Partial hydrosilylation of the aldehydes by the hydridosilanolate followed by the trimethylsilylation yields the alkoxydisiloxanes R'CH2OSiMe2OSiMe3 6 , 11. In some cases 2 partially reacts under hydrosilylation to give the alkoxydisilazanes R'CH2OSiMe2NHSiMe3 7,12.

The hydrosilylation is the preferred reaction of 1 and 2 with benzophenone. The compounds Ph2CHOSiMe2NHR 13, 14 are obtained. This difference in the reaction behaviour of 1 and 2 towards the aldehydes and benzophenone is mainly due to steric reasons. Depending on the conditions the imines Ph2C=NR 20, 21 may be formed. Ph2CHOSiMe2OSiMe3 (22) is a secondary product of imine formation.

In all reactions of 1 and 2 with the carbonyl compounds the corresponding alkoxysilanes R'CH2OSiMe3 (5: R' = CH2=C(Me), 6 : R' = Ph) and Ph2CHOSiMe3 (15) are generated.

Compounds resulting from a reaction of 1 and 2 with chlorotrimethylsilane are produced to minor extent, but only if the molar ratio of amide to carbonyl compounds is not greater than one. The formation of a silanimine intermediate in reaction according to B is not observed.
Complexation of Beryllium(II) by Maleic and Succinic Acid
Authors: Schmidt Michael , Bauer Andreas , Schier Annette , Schmidbaur Hubert
Published: February 2015

Abstract Beryllium succinate dihydrate [Be(C4H4O4)](H2O)2 is formed in the reaction of equimolar quantities of beryllium sulfate, succinic acid and barium hydroxide in aqueous solution at pH 3.2. Sodium, potassium, and ammonium bis(succinato)beryllates M2[Be(C4H4O4)2] are obtained using the same reagents in the molar ratio 1:2:1 and adjusting the pH to 6.3-6.5 with NaOH, KOH or concentrated aqueous ammonia, respectively. The corresponding potassium bis(maleato)beryllate is prepared similarly and obtained as a crystalline monohydrate, the structure of which has been determined by X-ray methods. The lattice contains spiro-bicyclic dianions with the Be atom chelated by two dicarboxylate ligands. The compounds undergo slow hydrolysis in water as shown by time-and pH-dependent 9Be NMR spectroscopy. In the neutral region (pH 6.5-6.9) the maleinato complexes are in an equilibrium with trinuclear compounds M3{[Be(C4H2O4)OH]3} as the predominating species, while in acid solution (at pH 1.3) only the aquo complex [Be(H2O4]2+ remains. In the intermediate pH region various complexes of the above types coexist, with only very slow ligand exchange (on the NMR time scale).
1.2.3.4-Tetrahydrochinoline als Substrate für Mannich-Verbindungen / 1.2.3.4-Tetrahydroquinolines as Substrates for Mannich Compounds
Authors: Möhrle H. , Tot E. , Rüdiger S.
Published: February 2015

The product of the reaction of 1,2,3,4-tetrahydroquinoline (1) with 2-naphthol (2) and form aldehyde reported as the N -substituted tetrahydroquinoline 3 show s really the structure of the phenylogous bis-substituted tetrahydroquinoline 4. The function of 1, 6 -methyl-1,2,3,4-tetrahydroquinoline (9) and 1-methyl-1,2 ,3 ,4 -tetrahydroquinoline (17) as amines or C -nucleophilic compounds in Mannich condensations were examined .
Über die Darstellung und spektroskopische Charakterisierung von (Me3SiO)3PH+I- / On the Preparation and Spectroscopic Characterization of (Me3SiO)3PH+I-
Authors: Minkwitz Rolf , Schneider Stefan
Published: February 2015

The reaction of Me3SiI with (Me3SiO)2P(O)H leads to tris(trimethylsiloxy)phosphonium iodide (Me3SiO)3PH+I- which has been characterized by vibrational and NMR spectroscopy.
Wechselwirkungen in Molekülkristallen, 144. ortho-Benzol-Derivate mit ineinander verzahnten Trimethylsilyl- Substituenten: Strukturvergleich mit Benzol-1,2-disulfonat-Salzen und Rotationsenthalpie-Hyperflächen/ Interactions in Molecular Crystals, 144, ortho-Benzene Derivatives with Meshed Cogwheel Trimethylsilyl Substituents: Structural Comparison with Benzene-1,2-disulfonate Salts and Rotation Enthalpy Hypersurfaces
Authors: Bock Hans , Nagel Norbert
Published: February 2015

ortho-Benzene derivatives with adjacent bulky propeller substituents are well-suited model compounds to investigate their potentially coupled rotations. To approach the molecular dynamics of 1,2-bis(trimethylsilyl)benzene, a liquid at room temperature and containing heteroelement substituents, an advantageous starting point are the crystal structures of the stereochemically correspondent benzene-1,2-disulfonate dianion salts. For both the rotations of the synperiplanar three-bladed rotor-groups -SO3
⊖ and -Si(CH3)3, PM3-enthalpy hypersurfaces are presented, which suggest only weak interdentate interaction and, concomitantly, only partly coupled intermolecular substituent rotation dynamics. Additional data from the Cambridge Structural Database for silicon organic compounds fit into the contour lines of the enthalpy surface calculated for 1,2-bis(trimethylsilyl)benzene, and the structure correlation with varying distances Si ···Si between the heteroelement centers can be discussed in more general terms of the substituent propeller blade length vs. thickness ratio.
Darstellung, 11B-und 19F-NMR-Spektren des Monofluoropentaiodo- closo-hexaboratanions sowie Kristallstruktur von (CH2Py2)[B6FI5]/ Synthesis, 11B and 19F NMR Spectra of the Monofluoropentaiodo-closo-hexaborate Anion and the Crystal Structure of (CH2Py2)[B6FI5]
Authors: Thomsen H. , Preetz W.
Published: February 2015

By reaction of closo-[B6H5F]2- in alkaline solution with excess iodine the monofluoropentaiodo- closo-hexaborate anion [B6FI5]2- is formed in good yield. The crystal structure of (CH2Py2)[B6FI5] has been determined by single crystal X-ray diffraction analysis (orthorhombic, space group Pnma, a = 13.803(2), b = 11.759(2), c = 13.936(2) Å, Z = 4). The B-F-bond length is 1.41 Å, the B-I distances range from 2.13 to 2.17 Å, the B-B distances from 1.69 to 1.76 A. According to the C4v point symmetry the 11B NMR spectrum of the anion exhibits three singlets at +3.8,-30.1 and-33.3 ppm with the intensity ratio 1:4:1, the 19F NMR spectrum one quartet at -247.6 ppm with the coupling constant 1J (19F, 11B) = 54 Hz.
Tuning the Steric and Electronic Properties of Chiral Rhenium Thiolate Complexes
Authors: Burzlaff Nicolai , Hagel Michael , Schenk Wolfdieter A.
Published: February 2015

Reaction of the complex [CpRe(NO)(CO)2]BF4 with triisopropylphosphine gives the chiral CO substitution product [CpRe(NO){P(i-Pr)3}(CO)]BF4. The corresponding triphenylphosphite complex [CpRe(NO){P(OPh)3}(CO)]BF4 may be obtained by oxidative CO removal. Reduction of the remaining CO ligand with NaBH4 furnishes the corresponding methyl com­plexes [CpRe(NO)(L)(CH3)]. The structure of [CpRe(NO){P(i-Pr)3}(CH3)] was determined: triclinic space group P1̄ (No. 2), a = 8.442(4), b = 9.582(5), c -11.820(8) Å, α= 81.81 (4), β = 87.18(4), γ = 63.87(5)°, Z = 2. Reaction of the methyl complexes with HBF4 in the presence of thiols gives, after chromatographic workup, the thiolate derivatives [CpRe(NO)(L)(SR)] (L = CO, P(OPh)3, P(i-Pr)3, R = CH2Ph, CH2(4-C6H4Cl), CH2(4-C6H4OMe), CH3, C2H5). The structure of [CpRe(NO){P(i-Pr)3}(SCH3)] was determined: monoclinic space group P21 (No. 3), a = 7.0515(7), b = 17.3469(10), c = 7.9727(7) Å, β = 114.021(7)°, Z = 2. In both structures, a significant opening of the angle N-Re-X (X = C, S) suggests that antibonding interactions between orbitals of the ligand X and the second-highest MO of the [CpRe(NO)(L)] complex fragment are avoided.
Thermochrome Chloro- und Bromocuprate: [C(NH2)3]2[CuBr4], (H3CC2N2SNH3)2[Cu2Br6], (C7N3H14)2[CuCl4], (C7N3H14)2[CuBr4], [(Cl, Br)C3N2H6][CuCl3OH2] und (BrC3N2H6)2[CuBr4] / Thermochromic Chloro- and Bromocuprates: [C(NH2)3]2[CuBr4], (H3CC2N2SNH3)2[Cu2Br6], (C7N3H14)2[CuCl4], (C7N3H14)2[CuBr4], [(Cl, Br)C3N2H6][CuCl3OH2] und (BrC3N2H6)2[CuBr4]
Authors: Díaz Isabel , Fernández Vicente , Martínez José Luis , Beyer Lothar , Pilz Astrid , Müller Ulrich
Published: February 2015

CuCl2 and CuBr2 were reacted in water-ethanol solutions containing HCl or HBr, respectively, with the following organic bases or their chlorides or bromides: guanidine (1), 2-amino-5-methyl-1,3,4-thiadiazol (2), hexahydro-2H-pyrimidine-(1,2A)-pyrimidine (3), and 2-hydrazino-2-imidazoline (4). With 1 and 3 the tetrahalocuprates (1H)2[CuBr4], (3H)2[CuCl4] and (3H)2[CuBr4] were obtained having flattened tetrahedral anions. 2 and CuBr2 form (2H)2[Cu2Br6], with nearly planar [Cu2Br6]2- ions that are associated to chains with squarepyramidal coordination of Cu. 2 and CuCl2 yield the hydrate (2H)Cl·H2O . 4 undergoes substitution of the hydrazine group for halogen, yielding the 2-halo-2-imidazolinium salts (5H)0,2(6H)0,8[CuCl3OH2] and (6H)2[CuBr4] in addition to [H3NCH2CH2NH3][CuCl4] (5 = 2-chloro-, 6 = 2-bromo-2-imidazoline). The planar [CuCl3(OH2)]- ions are associated to chains. Crystal structure determinations were performed with (1H)2[CuBr4], (2H)2[Cu2Br6], (3H)2[CuCl4], (5H)0,2(6H)0,8[CuCl3OH2] and (6H)2[CuBr4]; the latter three at 298 K and at 166 K or 173 K. The known crystal structure of [H3N(CH2)2NH3][CuCl4] was redetermined at 166 K. In all cases small differences of bond lengths and bond angles are observed between room temperature and low temperature. The magnetic properties and electrospray mass spectra were measured. The products show thermochromic behavior.
2-Bromo-5-iodo-hydroquinone and its Symmetrical and Unsymmetrical Dialkylethers
Authors: Höger Sigurd , Bonrad Klaus , Schäfer Gabriele , Enkelmann Volker
Published: February 2015

2-Bromo-5-iodo-hydroquinone dialkylethers are prepared by the stepwise halogenation and alkylation of hydroquinone monoalkylethers using simple and easily performable reactions. Boron tribromide induced cleavage of the dipropoyl ether gives the parent compound 2-bromo- 5-iodo-hydroquinone in good yields.
N-Benzoylthiocarbamoyl Amino Acid Ethyl Esters as Chelate Ligands for Transition Metal Ions
Authors: Leßmann Frank , Beyer Lothar , Richter Rainer , Meusinger Reinhard
Published: February 2015

The reactions of benzoyl isothiocyanate with amino acid ethyl esters (N-butyl glycine ethyl ester, (S)-(-)-proline ethyl ester) give N-benzoylthiocarbamoyl amino acid ethyl esters. Apart from the expected N-benzoylthiocarbamoyl (S)-(-)-proline ethyl ester the racemic N-benzoyl­ thiocarbamoyl (R)/(S)-proline ethyl ester is formed because of base catalyzed racemization of the educt (S)-(-)-proline ethyl ester during the reaction of (S)-(-)-proline ethyl ester hydrochloride with triethylamine. The structures of both compounds were established by X-ray crystal structure analysis and specific optical rotation measurements. The ligands yield neutral 2:1 chelates with NiII, CuII, PdII and PtII. The carboxylic oxygen atoms are not involved in the chelation. The ligands and the resultant complexes show configurational E/Z isomerism. In the case of the chelates of the racemic N-benzoylthiocarbamoyl (R)/(S)-proline ethyl ester, additional R/S isomerism is observed as shown by NMR spectroscopy.
1,2-Bis( 1′,3′ -dimethylimidazolin-2′-iminato)ethan - ein neuer Chelatligand [1] / 1,2-Bis(1′,3′-dimethylimidazolin-2′-iminato)ethane - a Novel Chelating Ligand [1]
Authors: Kuhn Norbert , Grathwohl Martin , Steimann Manfred , Henkel Gerald
Published: February 2015

The reaction of 2-imino-1,3-dimethylimidazoline (10, ImNH) with X-CH2CH2-X (11, X = p-CH3C6H4SO3) gives the diimine adduct ImN-CH2CH2-NIm · 2HX (12) from which the diimine ImN-CH2CH2-NIm (13) is obtained on treatment with KH. 13 reacts with (C6H5CN)2PdCl2 (15) to give the chelate complex (ImN-CH2CH2-NIm)PdCl2 (16). The X-ray structures of 12 and 16 are reported.
Benzo[b]fluorenes Formed in the Thermal Cyclization of 3-Ene-1,6-diynes
Authors: Schmittel Michael , Strittmatter Marc , Schenk Wolfdieter A. , Hagel Michael
Published: February 2015

A three-step preparation of the benzofluorene core is presented. The last step involves thermal cyclization of 3 -ene-1,6 -diyne (7) leading to the formation of four benzofluorene derivatives, one of which has been investigated by X-ray analysis. The harsh thermal conditions indicate that the cyclization of 7 might not proceed via a biradical intermediate as would be anticipated by a mechanistic proposal from Ueda.
Electron Donor-Acceptor Compounds. Synthesis and Structure of 5-(1,4-Benzoquinone-2-yl)-10,15,20-trialkylporphyrins
Authors: Runge Steffen , Senge Mathias O.
Published: February 2015

A series of 5-(benzoquinone)-10,15,20-trialkylporphyrins was synthesized via cross condensation of the respective aldehydes, 2,5-dimethoxybenzaldehyde and pyrrole followed by demethylation with BBr3 and oxidation with PbO2. This method worked reasonably well for compounds bearing the benzoquinone substituent and butyl, isopropyl, 1 -methylpropyl and 2-ethylpropyl residues (2a-d). The free base porphyrin quinones were converted into the zinc(II) complexes (3a-d) all of which showed remarkable stability for porphyrin quinones. The zinc(II) complex 3c bearing isopropyl residues was investigated by X-ray crystallography and showed a supramolecular structure consisting of polymeric chains facilitated by coordina­tion of a benzoquinone oxygen to a neighboring zinc(II) center. Attempts to synthesize a 5-(benzoquinone)-10,15,20-tris(terr-butylporphyrin) resulted in the formation of a yellow porphomethene (4), which could not be oxidized further. A crystal structure analysis of 4, the first for a free base porphomethene, shows an extremely twisted conformation with syn-orientation of the three tert-butyl groups. The results indicate that new methods will have to be developed for the synthesis of nonplanar porphyrin quinones.
Octacidomycine, IV : Neue Totalsynthese von rac-Octacidomycin und strukturverwandten Oligocarbonsäuren / Octacidomycins, IV : A New Total Synthesis of rac-Octacidomycin and Structurally Related Oligocarboxylic Acids
Authors: Krause Andreas , Lackner Helmut
Published: February 2015

Following a new strategy, an improved total synthesis of the unique antibiotic octacidomycin (1) and of structurally related oligocarboxylic acids was developed (Scheme 1,2). Starting from 3 and the tetraethylester of 1,17-dibromo-6,6,12,12-heptadecane-tetracarboxylic acid (6 ) as a key compound, systematical fragment condensations lead to the nonatriacontanepentadecacarboxylic acid 11 and hence to the 1,3,9,15,21,27,33,39-nonatriacontane-octacarboxylic acid 1. The synthetic pathway can easily be modified and generally be applied for the synthesis of a broad variety of hitherto unknown oligocarboxylic acids or their esters, respectively, and even of cyclic analogues (Scheme 2).
Ubergangsmetall-substituierte Phosphane, Arsane und Stibane, LX [1]. Ferrio-(thiocarbamoyl)phosphane Cp(OC)2 Fe-P(Mes)[C(=S)-N(R)H] (R = Me, Et, f-Bu): Aufbau aus dem Ferrio-mesitylphosphan Cp(OC)2 Fe-P(Mes)H und Organoisothiocyanaten sowie Quaternisierung mit Alkylhalogeniden und Oxidation mit Schwefel / Transition Metal Substituted Phosphanes, Arsanes and Stibanes, LX [1]. Ferrio-(thiocarbamoyl)phosphanes Cp(OC)2Fe-P(Mes)[C(=S)-N(R)H] (R= Me, Et, r-Bu): Build-up from the Ferrio-mesitylphosphane Cp(OC)2Fe-P(Mes)H and Organoisothiocyanates, Quatemization with Alkyl Halides and Oxidation with Sulfur
Authors: Malisch Wolfgang , Thirase Katharina , Reising Joachim
Published: February 2015

Arsane und Stibane, LX [1]. Ferrio-(thiocarbamoyl)phosphane Cp(OC)2Fe-P(Mes)[C(=S)-N(R)H] (R = Me, Et, f-Bu): Aufbau aus dem Ferrio-mesitylphosphan Cp(OC)2Fe-P(Mes)H und Organoisothiocyanaten sowie Quaternisierung mit Alkylhalogeniden und Oxidation mit Schwefel Transition Metal Substituted Phosphanes, Arsanes and Stibanes, LX [1]. Ferrio-(thiocarbamoyl)phosphanes Cp(OC)2Fe-P(Mes)[C(=S)-N(R)H] (R= Me, Et, r-Bu): Build-up from the Ferrio-mesitylphosphane Cp(OC)2Fe-P(Mes)H and Organoisothiocyanates, Quatemization with Alkyl Halides and Oxidation with Sulfur The ferrio-phosphane Cp(OC)2Fe-P(Mes)H (4), obtained by deprotonation of the me-sitylphosphane iron complex {Cp(OC)2 [H2(Mes)P]Fe}BF4 (3), reacts with the organoiso­ thiocyanates RNCS (R = Me, Et, Ph) (5a -c) to give the functionalized ferrio-phosphanes Cp(OC)2Fe-P(Mes)[C(=S)-N(R)H] (6a-c). Quatemization of 6a,b at the phosphorus atom with the alkyl halides R′-Hal (R1 = Me, Et, CH2 Ph) (7a-c) yields the complexes {Cp(OC)2Fe-P(Mes)(R′)[C(=S)-N(H)(R)]}Hal (8a-d), whereas oxidation with elemental sulfur affords the ferrio-thiophosphoranes Cp(OC)2Fe-P(=S)(Mes)[C(=S)-N(R)H] (R = Me, Et) (10a,b). 10b is alkylated with Mel to give {Cp(OC)2Fe-P(SMe)(Mes)[C(=S)-N(Et)H]}I (11). The structure of 8b has been determined by X-ray analysis.
Magnesium Bis[D(-)-Mandelate] Dihydrate and Other Alkaline Earth, Alkali, and Zinc Salts of Mandelic Acid
Authors: Schmidt Michael , Schier Annette , Schmidbaur Hubert
Published: February 2015

, and zinc D(-)mandelates have been prepared from the parent mandelic acid and equivalent quantities (1:1 / 2:1) of the corresponding metal hydroxides in water. Colourless polycrystalline products are obtained from the aqueous solutions by evaporation of the solvent. The alkali, ammonium and strontium salts are anhydrous, the calcium and barium salts are monohydrates, the magne­ sium salt is a dihydrate, and the zinc salt a trihydrate. The crystal and molecular structure of the magnesium salt has been determined by single crystal X-ray diffraction methods (mono­ clinic, space group P21, Z = 2). The lattice contains isolated complexes with hexacoordinate magnesium atoms chelated by two mandelate anions through one of their carboxylate oxygen atoms and the alcoholic hydroxyl group. Two water molecules in cis position are completing the octahedral coordination sphere. [Mg(C8H7O3)2(H2O)2] is thus a true mononuclear magnesium complex. Its stability and non-hygroscopic properties suggest its use as a magnesium and/or mandelate drug.
The Basicity of Silylamines and Alkylamines: An Equilibrium Study of the Competitive Borane Adduct Formation
Authors: Huber Gerald , Schmidbaur Hubert
Published: February 2015

In order to investigate the Lewis acid/base chemistry of silylamines in solution, the equilibrium reactions of Me3SiNMe2 / Me3SiNMe2(BH3) and different amines NR3 / amineboranes NR3(BH3) were monitored by 1H NMR spectroscopy in C6D6 and CDCI3 at 60 °C. For the equilibrium of the reference silylamine/-borane and Me3CNMe2 / Me3CNMe2(BH3) values K = 0.35 (AG = 3.1 kJ mol-1) in C6D6 and K = 0.50 (AG = 2.0 kJ mol-1) in CDCl3 have been estimated, showing that both the silylamine and the C/Si-analogous organic amine have very similar donor properties. Small amines like NMe3 proved to be much more powerful donors than the silylamine Me3SiNMe2, whereas bulky amines are less efficient donors, indicating that steric effects play an important role. The formation of BH3 adducts of Me2NSiH3 and (H3Si)3N which could not be followed experimentally owing to the low stability of the products, has been studied by quantum chemical calculations. A comparison with data for Me3N(BH3) shows that the silylamines are poorer donors, but the reason for this remains unclear
Kristallchemische Beziehungen von CO6O2 [TeO4 (CoAsO5)2] zur Steinsalzstruktur von CoO mit einem Beitrag über magnetische Messungen an CO6O2[TeO4(CoAsO5)2] / Crystal Chemical Relations of Co6O2[TeO4(CoAsO5)2] to the Rocksalt Structure of CoO and a Contribution on Magnetic Measurements of Co6O2[TeO4(CoAsO5)2]
Authors: Staack M. , Miiller-Buschbaum Hk.
Published: February 2015

The recently investigated compound Co6O2[TeO4(CoAsO5)2 marks the first occurrence of a tellurate-arsenate additionally revealing the hitherto unknown pyro-cobaltoarsenate group CoAsO7. One oxygen is exclusively connected to octahedrally coordinated cobalt. It is shown that the structure of Co6O2[TeO4(CoAsO5)2] can be derived step by step from the rock salt structure of CoO. Magnetic measurements using the Faraday technique reveal Curie-Weiss behaviour between 88 and 325 K. Low temperature measurements by a SQUID magnetometer show antiferromagnetism and a relatively low NEEL temperature of 5 K compared to other Co(II) compounds.
Untersuchungen an Polyhalogeniden, XXXVII [1]. Heptaiodide(3-) von Amminkomplexen des Chroms und Cobalts: Hexamminchrom(III)heptaiodid [Cr(NH3)6](I3)(I4) und die Tri-μ-hydroxo-bis[metall(III)-triammin]heptaiodide [(NH3)3 M(OH)3M(NH3)3](I3)2I mit M = Co, Cr / Studies o f Polyhalides, XXXVII [1]. Heptaiodides(3-) of Ammine Complexes of Chromium and Cobalt: Hexamminechromium(III) heptaiodide [Cr(NH3)6](I3)(I4) and the Tri-μ-hydroxo-bis[metal(III)-triammine] heptaiodides [(NH3)3M(OH)3M(NH3)3](I3)2I with M = Co, Cr
Authors: Tebbe Karl-Friedrich , Gilles Theo
Published: February 2015

The new compounds [Cr(NH3)6](I3)(I4) and [(NH3)3M(OH)3M(NH3)3](I3)2I with M = Cr, Co have been prepared by the reaction of [M(NH3)6]X3 (M = Cr, Co; X = Cl, I, NO3), KI, and I2 in water under controlled stoichiometric and pH conditions. The first compound is isotypic with the cobalt compound of the same composition. It crystallizes in the monoclinic space group I2/m with a = 984.7(3), b = 786.6(1), c = 1330.1(3) pm, β = 95.34(2)° and Z = 2 and contains nearly octahedral cations [Cr(NH3)6]3+, a linear triiodide ion I3
- and a tetraiodide ion I42-. The two other compounds are isotypic. They crystallize in the orthorhombic space group Pnma with a = 2629.6( 14) / 2633.5(2), b = 798.3(11) / 797.3(1), c = 1127.6(7) / 1125.7( 1) pm and Z = 4 for Co / Cr respectively. The heptaiodide(3-) ion is broken into two triiodide ions and one iodide ion
Thermische Zersetzung und Lösungskalorimetrie von Ammoniumeuropiumchloriden / Thermal Decomposition and Solution Calorimetry of Ammonium Europium Chlorides
Authors: Hennig C. , Oppermann H. , Blonska A.
Published: February 2015

The thermal decomposition equilibria of ammonium europium chlorides (NH4)3EuCl6, (NH4)2EuCl5 and NH4Eu2Cl7 have been investigated by total pressure measurements in a membrane zero manometer. The thermodynamic data of these solid phases have been derived from the decomposition functions. The standard enthalpies of solution in 4n HCl (aq.) of (NH4)3EuCl6, (NH4)2EuCl5, NH4Eu2Cl7, EuCl3 and Eu2O3 were measured. On the basis of these values and tabulated data, the standard enthalpies at 298 K of the ammonium europium chlorides were derived and compared with the obtained results from the total pressure measurements.
Photochemical Reductive Elimination of Nitrogen from Triazidogallium(III). Generation of Luminescent Gallium(I)
Authors: Kunkely Horst , Vogler Arnd
Published: February 2015

The irradiation of Ga(N3)3 in CH3CN leads to a reductive elimination of nitrogen according to the equation GaIII(N3)3 → GaIN3 + 3N2 (φ = 0.002 at λirr = 254 nm). Ga+ in CH3CN is characterized by its absorption (λmax = 298 nm) and emission (λmax = 475 nm) spectrum
Preparation and Crystal Structure of Cs4Nb2S11
Authors: Klepp Kurt O. , Gabi Gerald
Published: February 2015

The new polychalcogenide Cs4Nb2S11 was prepared from the melt. Cs4Nb7S11 is orthorhombic, oP68, s.g. Pca21 (No.29), Z = 4 with a = 13.775(9) Å, b = 8.043(9) A , c = 18.306(5) Å. The crystal structure was determined from diffractometer data and refined to a conventional R of 0.052 (1104 Fo’s, 154 variables). It is characterized by asymmetric discrete binuclear moieties [Nb2S11]4- which are separated by the alkali cations. Each Nb atom is side-on coordinated by two S2
2- groups, one bridging and one terminal sulfide ligand. Nb-S bond lengths are 2.15(1) Å to 2.22(1) Å (terminal) and 2.44(1 )Å to 2.51(1) Å (others). A further longer Nb-S bond (2.86(1)A and 2.90(1)A, resp.) expands the coordination of the two crystallographically independent transition metal atoms to distorted pentagonal bipyramidal configurations. The Nb-Nb-distance is 3.517(3) Å. The anionic groups are arranged in hexagonal close packed slabs running parallel to (001). The atomic arrangement corresponds to that of K4Ta2S11
Synthesis and Characterization of 1-Allyl-3,7,10-trimethylgermatrane and 1-Allylazagermatranes
Authors: Zaitseva Galina S. , Siggelkow Bettina A. , Karlov Sergey S. , Pen’kovoy Gleb V. , Lorberth Jörg
Published: February 2015

The reaction between Br3GeAll (1) and N(CH2CHMeOSnBu3)3 (2, mixture of isomers) yielded N(CH2CHMeO)3GeAll (3) as a mixture of diastereomers. Three azagermatranes of the type N(CH2CH2NR)3GeAll (9, R = H; 10, R = Me; 11, R = Me3Si) have been synthesized from the reaction of (Me2N)3GeAll (5) with N (CH2CH2NHR)3 (R = H, 6; Me, 7; Me3Si, 8). Composition and structures of the new compounds were established by elemental analyses, 1H and 13C NMR spectroscopy and mass spectrometry.
Mechanistische Untersuchungen zum reversiblen Gleichgewicht von metallorganischen Tripeldecker- und Sandwichkomplexen des Typs [Bis{(η5-CpR)Co}-μ-{η4:η4-aren}] und [(η5-CpR)Co(η6-aren)] / Mechanistic Studies towards the Reversible Equilibrium between Metal Organic Triple Decker and Sandwich Complexes [Bis{(η5 -CpR)Co}-μ-{η4 :η4-arene}] and [{(η5-CpR)Co(η6-arene)]
Authors: Schneider Jörg J. , Wolf Dirk
Published: February 2015

The arene ligand exchange mechanism of slipped arene triple deckers [Bis{(η5-CpR)Co}-μ-{η4:η4-arene}] (R = Me5, 1,2,4 tri-tert butyl, arene = benzene, toluene) 1 was studied by 1H-NMR spectroscopy for different concentrations and solvents. It has been found that triple deckers of type 1 decompose slowly in solution. A unique equilibrium, between these triple deckers and the mixed sandwich complexes [(η6-arene)Co(η5-CpR)] and 14 e [(η5-Cp)Co]solv fragments generated in situ by decomposition o f 1 exists. In addition to this equilibrium arene lability of the thus formed mixed sandwich complex type has been detected by NMR making slipped triple deckers 1 ideal single source compounds for the generation of two [(η5-Cp)Co] fragments in one reaction step. Such fragments are valuable metal ligand components with high synthetic utility in organometallic chemistry.
Synthesis of Glycosyl Cyanides by the Reaction of 1-S-Phosphorothioates of Carbohydrates with Trimethylsilyl Cyanide
Authors: Kudelska Wieslawa
Published: February 2015

A new procedure is described for the synthesis of α,β-glycosyl cyanides by the reaction of per-O-benzylated S-α-ᴅ-glycopyranosyl phosphorothioates with trimethylsilyl cyanide in the presence of Lewis acid. Starting S-glycosyl phosphorothioates are prepared, directly, from O-benzyl protected reducing D-hexopyranoses (gluco-, galacto-, manno-) and alkylammonium salt of phosphorothioic acid under Lewis acid catalysis.
Structure and Magnetic Properties of an Oxalic Acid Bridged Dinuclear Copper(II) Complex
Authors: Saha Manas Kumar , Sen Sutapa , Kundu Parimal , Gupta Tarakranjan , Gramlich Volker , Mitra Samiran
Published: February 2015

[LCu{μ-(OH)2(C2O2)}CuL](ClO4)2, (HL = N,N-dimethyl N-propylsalicylald-imine) was synthesised and its crystal structure was determined. C26H36CI2Cu2N4O14, triclinic space group P1̅ with a = 9.288(9), b = 10.016(11), c = 10.09(2) Å and a = 101.05(11), β = 108.22(10), γ = 110.22(10)°, V = 787(2) Å3, Z = 2. Two copper(II) ions in a distorted square-planar coordination are bridged by an oxalic acid molecule to form dinuclear units. The copper(II) centres are separated by 5.2 Å and antiferromagnetically coupled (J = -478 cm-1), which follows from temperature-dependent magnetic susceptibility measurements in the range 12 to 300 K.
2-Diphenylphosphino-phenoI as a Ligand for Mono- and Poly-Nuclear Complexes of Manganese, Cobalt, Nickel, Zinc, and Cadmium
Authors: Weiß Dana , Schier Annette , Schmidbaur Hubert
Published: February 2015

2-Diphenylphosphino-phenol was chosen as an ambivalent (hard/soft) chelating ligand for biologically important first row transition metals. The expected mode of complexation is relevant to trapping of metal ions in humic acids and related environmental ion exchange systems with phenolate functions. The 1:2 complex with nickel(II) is known to have a standard mononuclear square-planar structure, and experimental evidence suggests that the new cobalt(II) complex is analogous. By contrast, zinc and cadmium were found to give novel trinulear complexes [M3(2- Ph2P-C6H4O)6], M = Zn, Cd. In a chain of three metal atoms, the octahedrally coordinated central atom resides on a center of inversion and is solely oxygen-bound [MO6], while the two peripheral metal atoms are in a mixed coordination environment [fac-MO3P3], The analogous manganese(II) complex crystallizes as a net trihydrate, where two different trinuclear units are present in the lattice. One is of a new type and represents a centrosymmetrical hexahydrate [Mn3(2-Ph2P-C6H4 0)6(OH2)6]. The central part is an octahedral [Mn(OH2)6]2+ dication, which is hydrogen-bonded to two [Mn(2 -Ph2P-C6H4O)3]- anions. The nickel(II) complex was found to form 1:1 adducts with ZnCl2 or ZnBr2. The two complexes are isomorphous. In the adduct structure the zinc atom is attached to the two oxygen atoms of the nickel compound leaving the remainder of the molecular geometry largely unchanged. Together with the two halogen atoms a tetrahedral environment [ZnO2X2] is formed (X = Cl, Br), while the nickel atom retains its square planar [NiO2P2] environment.
Isolation and Structural Characterisation of Monoprotonated 1,2-Bis(diphenylphosphino)benzene in its Tetrabromogallate(III) Salt
Authors: Sigl Marcus , Schier Annette , Schmidbaur Hubert
Published: February 2015

Hydrolysis of gallium tribromide complexes of 1,2-bis(diphenylphosphino)benzene in toluene solvent affords crystals of the mono-phosphonium salt [ 1,2 -Ph2P-(C6H4)-PPh2H]+ [GaBr4]- . The structure analysis by single crystal X-ray diffraction allows an internal comparison of Ph2P phosphino and Pf2PH+ phosphonium functions.
Crystal Structure of Pyridinium Periodate
Authors: Dutkiewicz Grzegorz , Pająk Zdzisław
Published: February 2015

The crystal structure of the room-temperature ferroelectric phase of pyridinium periodate [C6H5NH]+[IO4]- has been determined by X-ray diffraction as orthorhombic, space group Cmc2i with a = 8.347(2), b = 7.270(2), c = 12.732(3) Å and Z = 4. It was refined to R1 =0.0281 wR2 = 0.0762 for 389 absorption-corrected reflections. The structure comprises isolated IO4 tetrahedra linked together by disordered pyridinium cations involved in a network of bifurcated hydrogen bonds. The average I-O distance is found to be 1.75(1) Å.
Darstellung und Kristallstruktur von /wer-[Os(NCS)3Py3] / Synthesis and Crystal Structure of mer-[Os(NCS)3Py3]
Authors: Kolf S. , Preetz W.
Published: February 2015

By reaction of K3[Os(NCS)3(SCN)3] with pyridine and glycerine the complex mer- [Os(NCS)3Py3] is formed. The X-ray structure determination on a single crystal (monoclinic, space group C2/c, a = 18.6156(12), b = 15.9448(7), c = 19.555(2) Å, β = 94.657(7)°, Z = 8) reveals that the nearly linear thiocyanate groups are exclusively bonded via the N atoms with Os-N-C angles ranging from 169.9° to 177.7°.
Nickel Complexes of N-Alkylated Derivatives of 2,6-Bis(aminomethyl)- 4-tert-butyl-thiophenol
Authors: Kersting Berthold
Published: February 2015

The syntheses of N-alkylated derivatives of the arenethiol 4-tert-butyl-2,6-(diaminomethyl)- thiophenol and their coordination properties are reported. Compounds 4-tert-butyl-2,6-di(N-isopropyl- aminomethyl)thiophenol (3) and 4-tert-butyl-2-(N-isopropyl-aminomethyl)-6-hydroxymethylthiophenol (6 ) react with Ni(II) salts to give compounds of composition [Ni(3)2]·2HCl (7) and [Ni(6)2] (8). The solid- and solution-state structures of both complexes consist of mononuclear complexes with four-coordinate nickel(II) ions in approximately planar trans- N2S2 coordination environments. In contrast to the parent arenethiol 4a, the sterically more encumbered ligands do not form dinuclear complexes.
The Molecular Structure of Tris(dimethylstibino)amine
Authors: Jockisch Alexander , Schmidbaur Hubert
Published: February 2015

Tris(dimethylstibino)amine N(SbMe2)3 is formed during reactions of sodium dimethylstibide with haloalkanes in liquid ammonia. It forms colourless monoclinic crystals, a = 12.108(1), b = 6.663(1), c = 16.891(2) Å, β = 10 1 .1 2 (1)°, P21/c, Z = 4, at -78 °C. The lattice contains independent molecules with a planar NSb3 core (sum of the angles at nitrogen 359.9°) and approximate C3h symmetry.
Die Kristallstruktur von N,N'-Ditosyl-/7-phenylendiamin, Dichtefunktionaltheorie-Berechnungen von Konformationen und Wasserstoffbrücken-Motive von Sulfonamiden / Interactions in M olecular Crystals, 146 [1, 2], The Crystal Structure of N,N'-Ditosyl-p-phenylenediam ine, Density Functional Theory Calculations of Conformations and Hydrogen Bond Motifs in Sulfonamides
Authors: Bock Hans , Nagel Norbert , Näther Christian
Published: February 2015

In a study preceeding the investigation of a novel class of inclusion compounds, the lowtemperature crystal structure o f the host-m olecule N ,N ’-ditosyl-p-phenylenediamine has been determined. It crystallizes in the monoclinic space group P21/N with two formula units in the unit cell, forming layers of hydrogen-bonded molecules. The essential subunits are rigid phenyl rings and flexible sulfonamide linkages C -N(H)-S(O2)-C, the conformations o f which are discussed by comparison with data from the Cambridge Structural Database and based on density functional theory (DFT) as well as semiempirical PM3 calculations for the selected model compounds, N-methyl-methane-, N-methyl-benzene- and N-phenyl-methane-sulfonamide. The torsion angle dependent energy and enthalpy profiles allow estimates o f the rotational barriers around the C -S-N -C bonds. In addition, potential hydrogen bonding by the host molecule is discussed in comparison to analogous carbonic acid derivatives.
Wechselwirkungen in Molekülkristallen, 149 [1 -3]. Wirt/Gast-Einschlußverbindungen von NjN'-Ditosyl-p-phenylendiamin: Die Wasserstoffbrücken-Addukte mit Morpholin; Pyridin, N,N-Dimethylformamid und Dimethylsulfoxid / Interactions in Molecular Crystals, 149 [1 - 3]. Host/Guest-Inclusion Compounds of N,N'-Ditosyl-/?-phenylenediamine: The Hydrogen Bonded Adducts with Morpholine, Pyridine, N ,N -Dimethylform amide, and Dimethylsulfoxide
Authors: Bock Hans , Nagel Norbert , Näther Christian
Published: February 2015

Basic principles of hyrogen-bonding are reviewed including cooperative effects and within the novel class of inclusion compounds formed by N,N′-ditosyl-p-phenylenediamine as a capable host, four aggregates with the hydrogen donor or acceptor guest molecules morpholine, pyridine, N,N-dimethylformamide and dimethylsulfoxide are reported. Morpholine introduces three additional hydrogen bonds N-H···N, N-H···O as well as C-H···O and pyridine, DMF and DMSO each one of type N-H···N, N-H··O(=C) and N-H···O(=S ). Crystallization and structures determined are discussed in detail with special emphasis on the varying sulfonamide conformation as well as on cavity or channel inclusion of the guest molecules. In conclusion, the crystal growth conditions and the structures of the altogether 13 N,N′-ditosyl-p-phenylenediamine inclusion compounds investigated are reviewed and possible reasons for their formation are discussed.