bluuebunny/crossref_metadata_2025 huggingface dataset:
Bromo-di(silyl)methanes - Precursors to Disilylcarbanionic Ligands
Authors: Bommers Sebastian , Beruda Holger , Paul Martin , Schmidbaur Hubert
Published: February 2015

The reaction of the series of methyl/phenylchlorosilanes Me2PhSiCl, MePh2SiCl and Ph3SiCl with CHBr3/n-BuLi to give the corresponding bromo-di(silyl)methanes has been investigated. The selectivity of the reaction proved to be strongly influenced by the number of phenyl groups bound to silicon. As already established for Me3SiCl, Si-C coupling readily occurs with Me2PhSiCl to give (Me2PhSi)2CHBr (1) in good yields, whereas MePh2SiCl affords (MePh2Si)2CHBr (2) in lower yields. The molecular structures of 2 and the by-product (MePh2Si)2CBr2 have been determ ined by single crystal X-ray diffraction. In the case of the fully arylated species, Ph3SiCl, only the monosilylated compound (Ph-Si)CH2Br (3) is generated. (HMe2Si)2CHBr (5) can be obtained starting from 1 by treatment with triflic acid to give (CF3SO3Me2Si)2CHBr (4), followed by reduction of 4 with LiAlH4 in diethyl ether. In situ metalation of 5 with n-BuLi affords (HMe2)2CHLi, which reacts instantaneously with a second equivalent of 5 to give the halogen-free dimer [(HMe2Si)2CH]SiMe2CH2SiMe2H (6).
Neue ternäre Vanadyl(IV) Komplexe mit ADP und AMP / New Ternary Vanadyl(IV) Complexes with ADP and AMP
Authors: Ferrer E. G. , Baran E. J.
Published: February 2015

Four new ternary VO2+ complexes, [VO HADP-dipy]. 6H2O , [VO HADP-ophen], 6H2O , [VO AMP-dipy], 6H2O and [VO AMP-ophen]. 6H2O (diny: α.α'dipyridyl; ophen: o-phenanthroline) were prepared and characterized by chemical analyses, electronic and vibrational spectra. Their bonding peculiarities are briefly discussed.
Phosphonic Acid Anhydrides [RPO2]n: Oligomerization and Structure
Authors: Fuchs Stefan , Schmidbaur Hubert
Published: February 2015

The phosphonic acid anhydrides of the general formula [RPO2]n have been prepared with R = Me, Et, i-Pr, t-Bu, and Ph from the corresponding phosphonic acids and their chlorides and esters. Mass spectrometric data indicate that the trimers are the dominant oligomers for all five systems. According to their NMR spectra, the methyl and t-butyl compounds have a symmetrical (C3v) structure with equivalent RP groups, while the ethyl, i-propyl and phenyl homologues have the Cs structure with non-equivalent PR groups in the ratio 1:2.
Poly[(tri-tbutyl-phosphine)gold(I)]ammonium Tetrafluoroborates and Bis(tri-tbutyl-phosphine)gold(I) Tetrafluoroborate
Authors: Sladek Alexander , Schmidbaur Hubert
Published: February 2015

The reaction of tris[(tri-tbutyl-phosphine)gold(I)]oxonium tetrafluoroborate with close to stoichiometric quantities of ammonia in dichloromethane at -78 °C affords tetrakis[(tri- tbutyl-phosphine)gold(I)]ammonium tetrafluoroborate, the structure of which has been determined by single crystal X-ray diffraction. The cation features a strongly distorted NAu4 tetrahedron with four short and two longer Au -Au edges. - With a large excess of ammonia, only partially aurated ammonium salts are formed, as suggested by detailed NMR spectroscopic and mass spectrometric studies. These partially aurated intermediates have not been isolated. Slow decomposition processes in these solutions lead to the precipitation of bis(tri- tbutyl-phosphine)gold(I) tetrafluoroborate. The structure of the bis(chloroform) solvate has also been determined. The crystals contain two independent C3-symmetrical cations with similar structures.
Crystal and Molecular Structure of Isonitrosomalonodiamido- (2,2-dipyridyl)copper(II), Chloride Monohydrate [Cu(Dipy){ONC(CONH2)2}Cl] · H2O
Authors: Yudin E. K. , Domasevitch K. V. , Rusanov E. B.
Published: February 2015

The crystal and molecular structure of the complex [Cu(Dipy){NDA}Cl] · H2O , where (NDA) = {ONC(CONH2)2}− anion (space group P 1̄, triclinic, with a = 7.834(1), b = 9.923(1), c = 9.952(1)Å, α = 93.60(1), β = 93.65(1), γ = 92.72(1)°, Z = 2) has been determined from X-ray diffraction data. The structure was refined to R = 0.029 for 2243 reflections with I>3σ(I). The coordination polyhedron of Cu2+ can be described as a distorted square pyramid with a chlorine atom in the apex, and with the central atom situated 0.258(3) A above the base of the pyramid towards the chlorine atom. The complicated system of hydrogen bonding involving the water of crystallization connects copper complex units in to the chains in the c direction.
Structures, Energies, Torsional Barriers, and Vibrational Spectra of Three Rotamers of Tetrasulfane, H2S4
Authors: Drozdova Yana , Miaskiewicz Karol , Steudel Ralf
Published: February 2015

Ab initio calculations at the MP2/6-311 G **//MP2/6-311 G** level show that the all-trans, cis-trans and all-cis rotamers of H2S4 are practically of identical energy. Their vibrational wavenumbers are also practically identical and in agreement with the observed infrared and Raman spectra of dissolved H2S4. On rotation about the central bond of H2S4 the torsional barriers are found to be 32.0 (cis -barrier) and 26.6 kJ mol-1 (trans-barrier). The geometries of the two transition states with τSSSS = 0° and 180° can be explained by hyperconjugation between the lone pairs at the terminal sulfur atoms and the σ * molecular orbital of the central bond.
The Ternary Rare Earth Chromium Nitrides Ce2CrN3 and Ln3Cr10−xN11 with Ln = La, Ce, Pr
Authors: Broil Sascha , Jeitschko Wolfgang
Published: February 2015

The title compounds have been prepared by annealing cold-pressed pellets of the binary nitrides LnN and CrN. Well developed crystals were obtained by recrystallization of the binary or prereacted ternary nitrides in a Li3N flux. Their structures were determined from single-crystal diffractometer data. C e2CrN3 has a U2CrN3 type structure: Immm , a = 379.0(1), b = 340.4(1), c = 1251.7(2) pm, Z = 2, R = 0.012 for 383 structure factors and 16 variables. The atomic positions of this structure are similar to those of U2IrC2 and K2NiF4. The structure may be rationalized to a first approximation with the formula (Ce+4)2[CrN3]8−. The chromium atoms are in a distorted square-planar nitrogen coordination. The CrN4-squares are linked via corner-sharing nitrogen atoms, thus forming infinite, straight - N - CrN2- N - CrN2- chains. The cubic structure of La3Cr10−xN11 (a = 1298.2(1) pm ), Ce3Cr10−xN11 (with a small homogenity range; a = 1284.3(1)-1286.1(3) pm ), and Pr3Cr10−xN11 (a = 1289.1(2) pm ) was determined for the lanthanum compound: Fm 3̄ m , Z = 8, R = 0.027 for 189 F values and 18 variables. One chromium site was found to have an occupancy of only 80.9(5)% resulting in the composition La3Cr9.24(1)N11. The nitrogen atoms occupy four atomic sites. Three of these have octahedral environments (6 La, 3 La + 3 Cr, 2 La + 4 Cr), the fourth one is surrounded by eight chromium atoms forming a cube. The chromium atoms are tetrahedrally coordinated by nitrogen atoms, and these CrN4-tetrahedra are linked via common corners and edges to form a three-dimensionally infinite polyanionic network. In addition the chromium atoms with oxidation numbers of about 2 to 3 form numerous Cr - Cr bonds, which allow to rationalize the Pauli paramagnetism of the compound.
Polysulfonylamine, LXV [1] Eine neue zentrosymmetrische Festkörper-Konformation von 18-Krone-6: Darstellung und Kristallstrukturen der monomeren Supramoleküle (CH2CH2O) 6 · 2 HN (SO2-2-Naphthyl)2 und (CH2CH2O) 6 · 2 iPrOH · 2 HN(SO2Ph)2 / Polysulfonylamines, LXV [1] A Novel Centrosymmetric Solid-State Conformation of 18-Crown-6: Synthesis and Crystal Structures of the Monomeric Supramolecules (CH2CH2O) 6 · 2 HN (SO2-2-Naphthyl)2 and (CH2CH2O) 6 · 2 iPrOH · 2 HN(SO2Ph)2
Authors: Henschel Dagmar , Näveke Martina , Hamann Thomas , Blaschette Armand , Jones Peter G.
Published: February 2015

The complexes 18 C 6 · 2 HN (SO2-2 -Naphthyl)2 (2a) and 18 C 6 · 2 iPrOH · 2 HN (SO2Ph)2 (3e) were obtained by co-crystallization of 18-crown-6 (18 C 6) with the appropriate di(arenesulfonyl) amine from isopropanol solutions at temperatures ≥20 °C (for 2a) or at - 20 °C (for 3e). Both structures contain isolated formula units displaying crystallographic inversion symmetry. The conformation of the crown rings is characterized by the torsion angle sequence g+g+aag−g+ag+ag−g−aag+g−ag−a, unprecedented in solid-state structures of 18C 6 complexes. The six ether oxygen atoms and four out of twelve carbon atoms of the ring are coplanar within ± 7 pm. In 2a (triclinic, space group P 1̄) , the disulfonylamine molecules are linked to the oxygen atoms of the g±g∓g∓ units via N -H ··· O hydrogen bonds ( H ··· O 201 pm, N - H ··· O 161°). In 3e (triclinic, space group P 1̄ ) , each amine is N - H ··· O bonded to an isopropanol molecule (H ··· O 193 pm , N - H ··· O 175°) that is connected to a crown oxygen atom of the same conformational type as indicated above for 2a (H ··· O 198 pm, O - H ··· O 166°).
Electroreduction of Organic Compounds, 25 Electrochemical Dehalogenation of Chlorinated Insecticides
Authors: Gassmann J. , Voss J. , Adiwidjaja G.
Published: February 2015

Partial but regio- and stereoselective dechlorination takes place if polychlorinated oligocyclic insecticides (Diels-Alder adducts and dimers of hexachlorocyclopentadiene) are electrolysed in methanol solution at lead cathodes. The products are detected and identified by GC/MS, IR and NMR spectroscopy. The structure of the product 2 formed from Mirex® is confirmed by an X-ray structural analysis.
Synthese von Nitrenkomplexen mit N-Trimethylsilylanilin I. Charakterisierung und Kristallstruktur von [Re(NPh)Cl3(Et2PhP)2] und [Re(NPh)Cl3(Ph3P)2] ·1/2 CHCl3 / Synthesis of Nitrene Complexes with N –T rimethylsilylaniline I. Characterisation and Crystal Structure of [Re(NPh)Cl3(Et2PhP)2] and [Re(N Ph)Cl3(Ph3P)2] · 1/2CHCl3
Authors: Wittern Ursula , Strähle Joachim , Abram Ulrich
Published: February 2015

trans-mer--Trichlorobis(diethylphenylphosphine)phenylnitrene rhenium(V), [Re(NPh)Cl3- (Et2PhP)2], has been synthesized from [ReOCl3 (Et2 PhP)2 ] and N-trimethylsilylaniline, while trans-mer-trichlorophenylnitrenebis (triphenylphosphine) rhenium(V), [Re(NPh)Cl3 (Ph3P)2] has been obtained via a novel route, from (Bu4N)[ReOCl4 ] and N-trimethylsilylanilin. The products were studied by mass spectrometry, IR spectroscopy and X-ray diffraction.

trans-mer-[Re(NPh)Cl3(Et2PhP)2 ] crystallizes in the monoclinic space group P21/n with a = 1498.5(3), b = 1068.6(1), c = 1784.0(4) pm and β = 91.28(1)°, Z = 4. The rhenium atom exhibits a distorted octahedral coordination with the phosphine groups in trans positions, and the Cl ligands in a meridional arrangement. The Re ≡N -C moiety is linear with a bond angle o f 169,4(5)°and a Re= N bond length o f 171.8(6) pm.

[Re(NPh)Cl3(Ph3P)2 ]· 0.5 CHCI3 crystallizes in the triclinic space group P 1̄ with a = 1232.1 (4), b= 1431.6(5), c = 2236.6(8) pm, a = 89.19(2)°, β = 80.50(2)°and γ = 88.26(2)°, Z = 4. The asymmetric unit contains two symmetry independent complex molecules of approximately the same structure, with Cl atoms meridionally arranged and the phosphine groups in trans positions. The coordination geometry is a distorted octahedron. The almost linear Re≡N -C moieties have Re≡N bond lengths of 170.2(7) and 170.8(7) pm, respectively, and Re≡N -C angles of 173.3(6)°and 175.0(7)°.
Darstellung, 11B-, 13C-, 29Si-NMR- und Schwingungsspektren von Trimethylsilylmethyl-hexahydro-closo-hexaborat, [B6H6(CH2Si(CH3)3)]- sowie Kristallstruktur von [P(C6H5)4][B6H6(CH2Si(CH3)3)] / Preparation, 11B, 13C, 29Si NMR and Vibrational Spectra of Trimethylsilylmethyl-hexahydro-clo-hexaborate, [B6H6(CH2Si(CH 3)3)]-and the Crystal Structure of [P(C6H5)4] [B6H6(CH2Si(CH3)3)]
Authors: Baurmeister J. , Franken A. , Preetz W.
Published: February 2015

By reaction of [N(C4H9 )4]2 [B6H6] with iodomethyl-trimethylsilane in acetonitrile a solution with trimethylsilylm ethyl-closo-hexaborate(1-)anions, [B6H6 (CH2Si(CH3)3)]-, is formed. The crystal structure of [P(C6H5 )4][B6H6(CH2Si(CH3)3)] has been determined by single crystal X-ray diffraction analysis; monoclinic, space group P21/n with a = 16.140(2), b = 11.646(8), c = 16.731(3) Å, β 109.664(11)°. The 11B NMR spectrum reveals features of a mono hetero substituted octahedral B6 cage. The 13C NMR spectrum exhibits a quartet at +0.18 ppm with 1J(C,H) = 118 Hz for the three methyl groups and a weak multiplet at -0.65 ppm for the methylene bridge due to quadrupole coupling with the boron atoms. In the 29Si NMR spectrum a decet at +2.25 ppm with 2J(C,H ) = 6.9 Hz is observed. The B -C stretching vibration is observed at 1155 cm-1 in the IR and Raman spectrum.
Tribochemical Synthesis and Study of Mixed Potassium-Ferrous Ferrocyanide and its RuII and OsII Analogs
Authors: Reguera E. , Fernández-Bertrán J. , Nuñez L.
Published: February 2015

Mixed potassium -ferrous ferrocyanide and its RuII and OsII analogs have been synthesized tribochemically by grinding Fe (SO4)·7H2O with the equivalent amount of K4[Fe(CN )6]·3H2O and the RuII and OsII compounds. Their XRD powder patterns and Mössbauer and IR spectra were recorded and interpreted. The role of hydration water on the feasibility of the tribochemical synthesis is discussed.
A Diosgenin Tetrasaccharide from Cestrum nocturnum
Authors: Ahmad Viqar Uddin , Baqai Fehmida T. , Ahmad Roshan
Published: February 2015

A new monodesmosidic spirostanol glycoside extracted from the fresh leaves of Cestrum nocturnum was identified as spirost-5-ene-3-ol, [3β,25R]-3-O-[{α-L-rhamnopyranosyl-(1→4)- α-L-rhamnopyranosyl-(1→2)}-α-L-rhamnopyranosyl-(1→4)-β-D-glucopyranoside. The name proposed for this saponin is nocturnoside B. The structure elucidation was done on the basis of 1 D and 2 D spectroscopic studies [DEPT. HeteroCOSY, HMBC, COSY-45°, HOHAHA ] and chemical analysis.
Structure of the Macrocyclic Bis-lactone Lepranthin from the Lichen Arthonia impolita; an X-Ray Analysis
Authors: Polborn K. , Steglich W. , Connolly J. D. , Huneck S.
Published: February 2015

The structure and relative stereochemistry of lepranthin from the lichen Arthonia impolita has been elucidated as 1 by NMR spectroscopy and X-ray analysis.
Ruthenium(II)-Komplexe mit neuartigen 1,10-Phenanthrolinliganden / Ruthenium(II) Complexes with New Kinds of 1.10-Phenanthrolin Ligands
Authors: Keuper Ralf , Risch Nikolaus
Published: February 2015

Different pathways to Ru-complexes are described using the hitherto unknown S-type terpyridines 3 and the known U-type ligands 4. The resulting hexafluorophosphates 6 and 7 have been spectroscopically characterized by 1H NMR and IR data and also by mass spectrometry and cyclic voltammetry.
1,2,3-Thiadiazole mit ungesättigten Seitenketten - Monomerbausteine für Photoresist-Materialien / 1,2,3-Thiadiazoles with Unsaturated Side Chains - Monomeric Building Blocks for Photoresists
Authors: Hanold Norbert , Kalbitz Helga , Al-Smadi Mousa , Meier Herbert
Published: February 2015

The phosphonium salts 4 are versatile reagents for the synthesis of 1,2,3-thiadiazoles 6 with unsaturated side chains. The preparation starts with the α-chloroketones 1 which are transformed in a stepwise process to the phosphonium salts 2 and 3. The reaction with SOCl2 leads to a regioselective ring closure 3 → 4 . Subsequent Wittig reactions yield the monomers 6, which exhibit with the exception of 6ac a high tendency for a thermal polymerization. Cleavage of the ester groups in 6ca and 6 cd generates the carboxylic acids 7ca and 7 cd which possess a higher stability.
Notizen: Tricarbonyliron Complexes - Observation of 13C(CO) NMR Signals via Polarization Transfer
Authors: Wrackmeyer Bernd , Köster Roland , Seidel Günter
Published: February 2015

Improvements in the detection of 13C(CO) resonances by using polarization transfer techniques, based on long-range coupling constants nJ(13C(CO)1H) = 1 ±0.1 Hz (n > 3), are reported. Coupling constants between 13C(CO) and other rare spin-1/2 nuclei have been observed, and longrange 13C(CO)-1H coupling have been traced by two-dimensional (2D ) 13C/1H heteronuclear shift correlations (HETCOR). Seven tricarbonyliron complexes 1 to 5 serve as examples in which the [Fe(CO)3] fragment is linked to cyclic dienes (siloles: 1a, b; 1,1′-spirobisilole: 2), and to cyclic heterodienes derived from substituted 2,5-dihydro- 2,5-silaboroles [1-aza (3a, b); 1-thia (4); 1-selena (5)]. In the case of complex 5, it was possible to resolve the 77Se satellites with 2J( 77Se13C(CO )) = 4.4 Hz. In 2D 13C (CO )/1H HETCOR experiments it was shown that polarization transfer originates mainly from C-methyl groups [4J( 13C(CO)/1H (M ))], adjacent to the “terminal” carbon atom(s) of the cyclic diene or heterodiene system which are linked to the [Fe(CO)3] fragment.
(1R,3R)-1,3-Dimethyl-8-hydroxy-6- methoxy-1,2,3,4-tetrahydroisoquinoline Hydrochloride - an Enantiomerically Pure Building Block for the Synthesis of Naphthylisoquinoline Alkaloids
Authors: Peters Karl , Peters Eva-Maria , Bringmann Gerhard , Keller Paul Anthony , Schäffer Manuela
Published: February 2015

The title compound was prepared by hydrogenolytic deprotection of the corresponding Nbenzyl derivative, which had previously been synthesized by a Picted-Spengler condensation of the corresponding arylethylamine. It crystallizes from dichloromethane/methanol in the orthorhombic system, space group P212121 ; a = 1305.7(2), b = 1400.3(3), c = 727.4(1) pm. Hydrogen bonds between Cl and OH and NH2 groups cause a threedimensional arrangement.
Darstellung und Kristallstruktur von [P(C6H5)4]Cl3 / Preparation and Crystal Structure of [P(C6H5)4]Cl3
Authors: Jansen M. , Strojek S.
Published: February 2015

Preparation and crystal structure of [P(C6H5)4]Cl3 are reported. [P(C6H5)4]Cl3 crystallizes in the monoclinic space group P21/c with a = 1093.4(4), b = 789.1(1), c = 2682.7(7) pm, β = 90.39(1)°, V = 2200.27·106 pm3, and Z = 4. The geometry of the trichloride anion in the solid state is almost linear (Cl-Cl-Cl = 178.44(4)°) and unsymmetrical (d(Cl-Cl) = 226.3(1) and 230.7(1) pm).
Derivate des Hydrazins als Liganden in Vanadium(IV)- und -(V)-Komplexen. Darstellung und Struktur dreier dimerer Verbindungen mit Hydrazido- und Hydrazonato-Liganden / D erivatives of H ydrazine as Ligands in V anadium (IV ) and -(V) Complexes. Synthesis and Crystal Structures of Three D im eric C om plexes with H ydrazido and H ydrazonato Ligands
Authors: Kopka Klaus , Mattes Rainer
Published: February 2015

The complexes [(μ-PhCONNCOPh){VOCl(NHNHCOPh)}2 ·5CH3CN, (1), [(μ-PhCONNCOPh){V(dbh)}2]-2CH3CN, (2) and [{VO}2(tbh)], (3) have been prepared by reaction of VCl2(acac)2, acac = acetylaceto n a to (l-), and VCl2(acpn), acpn = propylendiim ino-bis(acetylacetonato(2-)), with benzoylhydrazine. The structures of the centrosymmetric dimeric molecules 1 -3 have been determined by single crystal X-ray diffraction. 1 and 2 contain both doubly deprotonated N,N′-dibenzoylhydrazine as bridging, doubly N,O chelating ligand. In 1 the two remaining coordination sites at the VOCl group are occupied by the hydrazid o(1-) ligand [NHNHCOPh]- . 2 is a non-oxo vanadium(IV) complex. The coordination geometry is approximately trigonal prismatic. The π-back donating effect of the oxo function is substituted by back donation from three negatively charged enolic oxygen atoms. The V - O bond lengths range from 192.0(2) to 193.7(2) pm. 3 contains a unique highly symmetrical octadentate ligand, formed during the synthesis. It is coordinated to two oxovanadin(IV) centers by N,O chelation. The coordination geometry is square pyramidal.
Funktionalisierte tripod-Liganden mit Neopentan-Grundgerüst: Umsetzung von HOCH2C(CH2PR2)3 mit Elektrophilen / Functionalized tripod-Ligands with N eopentane Fram ew ork: R eaction of HOCH2C(CH2PR2)3 with Electrophiles
Authors: Seitz Thomas , Asam Alexander , Hüttner Gottfried , Walter Olaf , Zsolnai Laszlo
Published: February 2015

Several ways to functionalize hydroxy-tripod-ligands (HOCH2C(CH2PR2)3) by activation with electrophiles are presented. The use of carboxylic halides and anhydrides is shown to be generally successful for esterification reactions in a one-pot synthesis starting from the oxetanes O(CH2)2C(CH2PR2)2. Facial coordinaton of the related esters towards iron(II) and molybdenum(O) can be achieved depending on the nature of the phosphane donor groups.

If methyliodide or trimethylsilylchloride are used as electrophiles in order to functionalize the hydroxy group in HOCH2C(CH2PR2)3, it is necessary to proctect the phosphane groups by formation of the tris-borane adduct.

All new compounds have been fully characterized by the usual analytical techniques as well as by X-ray analyses on selected examples.
Synthesis, Vibrational Spectra, Mass Spectrum and Crystal Structure of Tri-n-butyltin Diphenylphosphinate (n-Bu)3SnO2PPh2
Authors: Shihada Abdel-Fattah , Weller Frank
Published: February 2015

Tri-n-butyltin diphenylphosphinate (n-Bu)3SnO2PPh2 has been synthesized by the reaction of (n-Bu3Sn)2O with Ph2POCl in toluene. An X-ray diffraction study of (n-Bu3)SnO2PPh2 shows that the structure is polymeric and consists of helical chains in which (n-Bu)3Sn groups are linked by O-P-O bridges. The geometry about tin is trigonal bipyramidal, with n-butyl groups in equatorial positions and an axial O-Sn-O angle of 176.2 (2)°. IR and Raman spectra of (n-Bu)3SnO2PPh2 are given and assigned. The mass spectrum is reported and discussed.
Neue Niob- und Tantalchloride der Zusammensetzung A4[M6Cl18] (A = (Ga,) In, TI; M = Nb, Ta) / New Niobium and Tantalum Chlorides of the Composition A4[M6Cl18] (A = (Ga,) In, TI; M = Nb, Ta)
Authors: Baján Béla , Meyer H.-Jürgen
Published: February 2015

The syntheses of new compounds of the general formula A4[Nb6Cl18] (A = Ga, In, Tl) and A4[Ta6Cl18] (A = In, Tl) are reported. The indexing of their X-ray powder patterns was performed isotypically with K4Nb6Cl18]- A single-crystal structure refinement on In4[Ta6Cl18] gave the space group C2/m, Z - 2, a = 1077.7(3) pm, b = 1542.3(5) pm, c = 960.2(2) pm, β = 117.68(2) . The structure contains [Ta6Cl12Cl6]4- ions linked via I+ ions . In+ is situated in a strongly distorted coordination sphere of Cl- .
Carben- und Carbin-Komplexe des Technetiums und Rheniums - Synthese, Struktur und Reaktionen / Carbene and Carbyne Complexes of Technetium and Rhenium - Synthesis, Structure and Reactions
Authors: Fischer Ernst Otto , Apostolidis Christos , Dornberger Ernst , Filippou Alexander C. , Kanellakopulos Basil , Lungwitz Bernhard , Müller Jakob , Powietzka Bernhard , Rebizant Jean , Roth Werner
Published: February 2015

Synthesis, structure and reactions of technetium and rhenium complexes bearing metal-carbon multiple bonds are reported. Addition of LiPh to Cp*M (CO)3 (1a : M = Tc; 1b: M = Re) (Cp* = η5-C5Me5) in Et2O yields the acyl complexes Li[Cp*(CO)2MC(O)Ph]·Et2O (2a: M = Tc; 2 b: M = Re). These are converted with Et3OBF4 into the carbene complexes Cp*(CO)2M = C(OEt)Ph (3a, 3b). Reaction of 3a and 3 b with BCl3 affords the carbyne complexes [Cp*(CO)2M ≡ CPh]BCl4 (4a, 4b) in high yield. The acyl complex 2b can be directly converted into the carbyne complex [Cp*(CO)2Re ≡ CPh]Br (5b), when it is treated with oxalyl bromide. Nucleophiles add at the carbynecarbon atoms of 4a and 4b, as demonstrated by the reaction with NaOCy (Cy = cyclohexyl) to afford the carbene complexes Cp*(CO)2M = C(OCy)Ph (6a, 6b). Similarly, reaction of P(OMe)3 with [Cp*(CO)2Re ≡ CPh]Cl (5b'), the latter being generated in situ from 2b and oxalyl chloride, gives the ylide complex {Cp*(CO)2Re = C[P(OMe)3]Ph}Cl (7b'). In comparison, addition of P(OMe)3 to [Cp*(CO)2Tc ≡ CPh]Cl (5a'), generated in situ from 2a and oxalyl chloride, induces a carbvne-carbonvl coupling reaction resulting in the formation of the ketenyl complex

. Thermolysis of the compounds 2a, 2b, 4a, 4b and 7b' has been studied in vacuo and the products of decomposition identified by IR spectroscopy. The solid-state structure of the carbene complexes 3 a and 3 b was determined by single crystal X-ray diffraction studies. Both compounds crystallize in the monoclinic space group P21/n with very similar unit cell data. Striking feature of the isostructural carbene complexes is the nearly perpendicular orientation of the carbene ligand relative to the Cp* ring.
Transition State Geometry and Solvent Effects in the Enantioselective Oxidation of Sulfides to Chiral Sulfoxides by Oxaziridines
Authors: Pointner Andreas , Herrmann Rudolf
Published: February 2015

For the enantioselective oxidation of methyl phenyl sulfide and tert-butyl methyl sulfide to the corresponding chiral sulfoxides by 3,3-dibromo-(camphorsulfonyl)oxaziridine, semiempirical calculations (MNDO, AMI, PM3) concerning transition state geometries were performed. The results show that only PM3 is able to localize a transition state. For methyl phenyl sulfide, a spiro arrangement of the oxaziridine ring and the sulfur atom explains the observed direction of the selectivity better than a planar transition state. The solvent dependence of the observed enantioselectivity is related to the calculated dipole moment of the transition state by the Kirkwood-Onsager model. In THF as solvent, its direct participation in the transition state has to be considered
Notizen: Sodium Metaperrhenate, NaReO4: High Pressure Synthesis of Single Crystals and Structure Refinement
Authors: Atzesdorfer Alexandra , Range Klaus-Jürgen
Published: February 2015

Single crystals of sodium metaperrhenate, NaReO4, have been obtained by oxidation of rhenium metal with sodium nitrate under high pressure- high temperature conditions (modified Belttype apparatus, 4 kbar, 400 °C, Au-capsules). The crystals are tetragonal, space group I41/a, with a = 5.3654(4), c = 11.732(2) Å and Z = 4.

The structure was refined to R - 0.026, Rw = 0.013 for 382 unique, absorption-corrected reflections. The scheelite-type structure for NaReO4, proposed by Beintema in 1937, could be confirmed. It consists of isolated ReO4 tetrahedra (Re-O= 1.728(2) Å ), connected by NaOs dodecahedra ( = 2.582(2) Å).
Ionische Phosphaniminato-Komplexe von Schwefel(IV) und Selen(IV ). Die Kristallstrukturen von [S(NPMe3)3]Cl · CH2Cl2, [S(N PPh3)3]S4N5 und [Se(NPMe3)3]Cl · C7H8 / Ionic Phosphorane Iminato Complexes of Sulfur(IV) and Selenium(IV). Crystal Structures of [S(NPMe3)3]Cl ·CH2Cl2, [S(NPPh3)3]S4N5 and [Se(NPMe3)3]Cl · C7H8
Authors: Kunkel Frank , Folkerts Hella , Wocadlo Sigrid , Kang Hak-Chul , Massa Werner , Dehnicke Kurt
Published: February 2015

[S(NPMe3)3]Cl · CH2C12 and [S(NPPh3)3]S4N5 were prepared by the reaction of Me3SiNPMe3 or Me3SiNPPh3 with sulfur dichloride and S3N2Cl2, respectively, in CH2Cl2 solutions as colourless, moisture sensitive crystals. The corresponding selenium compound was prepared from SeCl4 and Me3SiNPMe3 in acetonitrile solution; it crystallizes from toluene solutions with one mole of toluene per formula unit. All complexes have been characterized by IR spectroscopy and by crystal structure determinations.

[S(NPMe3)3]Cl-CH2Cl2: Space group Pna21, Z = 8 , 3930 observed unique reflections, R = 0.033. Lattice dimensions at -120 °C: a = 1200.9(1), b = 1020.2(1), c = 1790.5(1) pm.

[S(NPPh3)3]S4N5: Space group P63, Z = 2, 2586 observed unique reflections, R = 0.054. Lattice dimensions at -100 °C: a = b = 1334.7(2), c = 1652.6(2) pm.

[Se(NPMe3)3]Cl · C7H8: Space group C2/c, Z = 8 , 1475 observed unique reflections, R = 0.059. Lattice dimensions at -40 °C: a = 1853.6(8), b = 1159.2(4), c = 2053.2(4) pm. β = 101.92(3)°.

All compounds contain cations [E(NPR3)3]+ (E = S, Se) with pyramidal structures. Bond lengths and bond angles are in average: S-N 162.5 pm, S-N-P 120.5° (R = Me), S-N 161.8 pm, S-N-P 119.2° (R = Ph), Se-N 177.8 pm, Se-N-P 120.3°.
Kristallstruktur des cyanoverbrückten polymeren Zinkcyanid-Pyridin-Komplexes [Zn(py)2][Zn(CN)4] / Crystal Structure of the Cyano Linked Polymeric Zinc Cyanide Pyridine Complex [Zn(py)2][Zn(CN)4]
Authors: Pickardt Joachim , Staub Benedikt
Published: February 2015

The reaction of aqueous solutions of potassium tetracyanozincate, zinc chloride, and pyridine yields crystals of [Zn(py)2][Zn(CN)4], The crystals are orthorhombic, space group Cccm, a = 926.7(4), b = 1340.8(4), c = 1343.3(4) pm. The structure is polymeric and consists of alternate arrays of tetrahedrally and octahedrally coordinated zinc atoms, bridged by CN ligands. Two pyridine molecules ligate at the axial positions of the octahedrally coordinated zinc atoms.
2-YIidvl-1,3,2-oxathiaphosphole und -oxaselenaphosphole / 2-Ylidyl-1,3,2-oxathiaphospholes and -oxaselenaphospholes
Authors: Schmidpeter Alfred , Plank Stefan , Polborn Kurt
Published: February 2015

Ylidyl thioxophosphines or selenoxophosphines and phenacyl halides undergo addition in a 1:1 ratio and yield in the presence of triethylamine the title compounds. The molecular structure of an ylidyl oxathiaphosphole demonstrates a strong interaction between the ylid substituent and the heterocycle, making the exocyclic PC-bond unusually short and the endocyclic PO- and PS-bonds considerably longer than normal for a pyramidal phosphorus atom.

The ylidyl chalcogenoxophosphines are oxidized by sulfur or selenium at the phosphorus atom and protonated at the ylidic carbon atom. No Wittig-type reaction is observed.
[Er14(C2)2(N)2]l24 – ein Iodid mit einem oligomeren, heterointerstitiellen Cluster / [Er14(C2)2(N)2]l24 – an Iodide with an Oligomeric, Heterointerstitial Cluster
Authors: Steffen Frank , Meyer Gerd
Published: February 2015

[Er14(C2)2(N)2]l24 (triclinic, P1̅, a = 966.3(4) pm. b = 1027.6(2) pm. c = 1663.4(4) pm, α = 101.374(9)°, β = 92.853(14)°, γ = 112.83(2)°, Z = 2) is obtained as red-brown single crystals through a conproportionation reaction of Erl3 and erbium in the presence of carbon and NaN3 in a sealed niobium container. It contains discrete, tetrameric [Er14(C2)2(N)2] clusters that are built from two octahedra and two tetrahedra connected via common edges. The octahedral voids are filled with C2 units and the tetrahedral voids with N atoms. Each discrete [Er14(C2)2(N)2] cluster is surrounded by 32 iodide ligands which connect six clusters via i-a and a-a bridges.
Formation and Identification of Bis[bis(trimethylsilyl)amino]triand tetrachalcogenides
Authors: Siivari Jari , Maaninen Arto , Haapaniemi Esa , Laitinen Risto S. , Chivers Tristram
Published: February 2015

The reaction of (Me3Si)2NLi with SCl2 and elemental sulfur or with Se2Cl2 and elemental selenium leads to the formation of mixtures of bis[bis(trimethylsilyl)amino]suIfides and selenides [(Me3Si)2N]2Ex (E = S or Se; x = 1 - 4 ). The reaction products were identified by mass spectroscopy as well as by 77Se and 13C NMR spectroscopy. The reaction of (Me3Si)2NH with S2Cl2 produces [(Me3Si)2N]2S3 as the main product with only traces of other aminosulfides. [(Me3Si)2N]2S3 was purified by distillation under reduced pressure and identified by elem ental analysis, mass spectroscopy, and by 1H, 13C, and 14N NMR spectroscopy. The successful cyclocondensation reaction of [(Me3Si)2N]2S3 with SCl2 and SO2Cl2 produces S4N2 in 72% yield and provides further verification of the identity of bis[bis(trimethylsilyl)amino]trisulfide. While the analogous reaction of (Me3Si)2NH with Se2Cl2 also leads to the formation of [(Me3Si)2N]2Se3 (48 mol %) as the main product, the reaction mixture contains [(Me3Si)2N]2Se2 and [(Me3Si)2N]2Se4 in significant amounts (17 and 35 mol %, respectively). Attempts to purify the mixture by distillation under reduced pressure resulted only in the formation of a 83:17 mixture of [(Me3Si)2N]2Se2 and [(Me3Si)2N]2Se3.
New Observations Concerning the Reactivity of Triorganotin Fluorides
Authors: Lambertsen Thomas , Schmutzler Reinhard
Published: February 2015

Me3SnF (1) reacts with many hydrolyzable chlorides to give Me3SnCl and the corresponding fluoride. The formation of PhPF2, (ClCH2)MeSiF2, F2PCH2PF2 and PF5 is described. The reaction of triorganotin fluorides (Ph3SnF, Bu3SnF) with CaBr2 yields pure triorganotin bromides. 1 was found to act either as a fluoride-acceptor or, towards PF5, as a fluoride-donor.
Kaliumgraphit - ein effizientes Reduktionsmittel zur Darstellung von Polysilinen / Potassium-Graphite - an Efficient Reducing Agent for the Formation of Polysilynes
Authors: Uhlig Wolfram
Published: February 2015

Potassium-graphite (C8K) reduces phenyltrichlorosilane to give polyphenylsilynes in high yields. Branched copolysilanes have been prepared via reductive coupling of phenyltrichlorosilane and diorganodichlorosilanes with C8K. Polymers of this type are also obtained by reductive coupling of triflate substituted polysilanes with C8K. The soluble polymers and copolymers with molecular weights in the range ≈ 4000 to 10000 have been characterized by 29Si-NMR spectroscopy.
Elektronentransfer und Kontaktionen-Bildung, 42 [1,2] Cyclovoltammetrische und ESR / ENDOR-Untersuchungen der Einelektronen-Reduktion von Diphenochinonen / Electron Transfer and Contact Ion Pair Formation, 42 [1,2] Cyclovoltammetric and ESR / ENDOR Investigations of the One-Electron Reduction of Diphenoquinones
Authors: John Andreas , Bock Hans
Published: February 2015

Semiquinone radical anions are prototype compounds for contact ion pair formation with metal counter cations. In order to investigate the still open question whether bulky alkyl groups can sterically interfere, diphenoquinone derivatives O=C(RC=CH)2C=C(HC=CR)2C=O with R = C(CH3)3, CH(CH3)2 and CH3 have been selected and the following ESR/ENDOR results are obtained for the alkaline metal cations: The tetrakis(tert-butyl)-substituted radical anion only adds Li⊕ and Na⊕, while K⊕ forms no ion pair. The 3,3ʹ,5,5ʹ-tetra(isopropyl)diphenoquinone radical anion is accessible to all cations Me⊕, although Rb⊕ and Cs⊕ seem to be present solvent-separated in solution. The tetramethyl-substituted radical anion unfortunately polymerizes rapidly. Additional information concerns the ESR/ENDOR proof for ion triple radical cation formation [Li⊕ M•⊖Li⊕]•⊕, or the difference in the coupling constants upon Me⊕ docking at one δ⊖O=C group, suggesting that about 87% of the spin density is located in the cation-free molecular half of the diphenoquinone radical anion. Based on the wealth of ESR/ENDOR information, crystallization of the contact ion pairs and their structural characterization should be attempted.
Impedance Measurements to Determine the Influence of Fluoride at Platinum Anodes During the Formation of Peroxodisulfate
Authors: Scheler Irene , Wabner Dietrich W.
Published: February 2015

The electrode reactions at platinum anodes in 1.5 M H2SO4 + 2.3 M (NH4)2SO4 solution with and without addition of NaF (0.5 M) have been examined. Impedance spectra between 1 to 100.000 Hz were measured under galvanostatic conditions. Electrolyte, polarization, chargetransfer resistance (RD), double-layer capacitance (CD) and inductance (L) were determined.

For a constant current density, fluoride causes an increase o f CD and a decrease of RD. At a certain potential (measured and corrected by the electrolyte resistance) CD nearly remains the same with and without fluoride, whereas RD is slightly increased by fluoride.

This behaviour is explained by the double function o f the fluoride: It is adsorbed on the anode surface and causes an increase o f the real current density on the surface. Simultaneously, the evolution o f oxygen is hindered by fluoride.
Suspension NMR Spectroscopy of Phosphines and Carbonylnickel Complexes Immobilized on Silica
Authors: Behringer K. D. , Bliimel J.
Published: February 2015

The 31P suspension NMR spectra o f silica-immobilized bifunctional phosphines and their di- and tricarbonylnickel complexes were recorded using conventional high resolution NMR equipment. The practical advantages of suspension NMR spectroscopy, as compared to 31P CP/MAS NMR spectroscopy, are discussed. General tendencies are demonstrated: The suspension NMR signals become broader with increasing solvent viscosity and decreasing solvent polarity. Phenyl groups as spacers lead to broader resonances than alkyl chains. The linewidths increase in the case of chelation.
Synthese und Struktur von 2-Imino-1,3-dimethylimidazolin / Synthesis and Structure of 2-Imino-1,3-dimethylimidazoline
Authors: Kuhn Norbert , Fawzi Riad , Steimann Manfred , Wiethoff Jörg , Bläser Dieter , Boese Roland
Published: February 2015

Deprotonation of the 2-amino- 1,3-dimethylimidazolium salt 5 (obtained through methylation of 2-amino-l-methylimidazole (4)) by KH gives 2-imino-1,3-dimethylimidazoline 6. The trimethylsilylimino compound 14 is formed on the reaction of 6 with chlorotrimethylsilane in the ratio 2:1. Further reaction with chlorotrimethylsilane gives the silylated aminoimidazolium salt 15. The X-ray structures of 5 and 6 are reported.
Synthese und Eigenschaften von N-phosphorylierten Aminomethylen-dimethylphosphinoxiden und -sulfiden / Synthesis and Properties of N-Phosphorylated Aminomethylene-Dimethylphosphine Oxides and -Sulfides
Authors: Kaukorat Thomas , Neda Ion , Schmutzler Reinhard
Published: February 2015

In the reaction of N-methylaminomethylene-dimethylphosphine oxide and sulfide with diethylaminotrimethylsilane, N-methyl-N-trimethylsilyl-aminomethylene-dimethylphosphine oxide (1) and sulfide (2) were formed. These compounds were allowed to react with a series of P(III)C1 compounds to give the corresponding methylaminomethylene-bridged diphosphorus compounds (3 - 10) with phosphorus in the combination λ4P(V)/λ3P(III). In the oxidation of some of these compounds by the hydrogen peroxide-urea 1:1-adduct (NH2)2CO ·H2O2 or sulfur, the corresponding λ4P-CH2-N(Me)-λ4P-derivatives (11 - 16) were formed. Different reaction behaviour was observed depending on the substituent at λ4P or on the oxidizing agent. Reaction of 1 with trimethylsilylmethyl tetrafiuorophosphorane and with bromotriphenylphosphonium bromide furnished, besides trimethylhalosilane, the corresponding diphosphorus compounds (17 ) and (18) with phosphorus in the combination λ4P(V)/λ5P(V) (17) and λ4P(V)/λ4P(V)+ (18).

Oxidation of N-diphenylphosphino-N-methyl-aminomethylene-dimethylphosphine oxide (3) by tetrachloro-o-benzoquinone led to the corresponding addition product in impure form. Reaction of 3 with hexafluoroacetone (HFA) yielded a mixture of two products which could not be separated. Both oxidation (>N-PPh2 → >N-P(:O)Ph2) and insertion of HFA into the P-N-bond (>N-PPh2 → >NC(CF3)2-O-PPh2) occurred. In the reaction of 1 with methyldichlorophosphine, both the mono- and disubstituted products, 22 and 23, were formed, independently of the reaction conditions and molar ratio of the starting compounds. The reaction of 1 with bis(diethylamino)chlorophosphine was unusual. Upon separation of both trimethylchlorosilane and dimethylaminotrimethylsilane, compounds 24 - 26 were formed, with the central phosphorus atom bearing one, two or three methylaminomethylene-dimethylphosphine oxide groups, respectively. Simultaneously, tris(diethylamino)phosphine was formed.
Vier verschiedene Koordinationspolyeder um Cu2+ im Oxid-Arsenat-Phosphat CuO(Cu,Mg)3(As1–xPxO4)2 (x = 0,3) / Four Different Coordination Polyhedra Around Copper in the Oxide-Arsenate-Phosphate CuO(Cu,Mg)3(As1-xPxO4)2 (x = 0,3)
Authors: Frerichs D. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of CuO(Cu,Mg)3[(As0.7P0.3)O4]2 have been prepared by crystallization from melts. The compound crystallizes with triclinic symmetry, space group Ci
1-P1̄, a = 6.372(4), b = 7.643(7), c = 8.175(5) Å, α = 98.59(6), β = 112.26(3), γ = 99.03(3)°, Z = 2. CuO(Cu,Mg)3[(As0.7P0.3)O4]2 is isotypic to Cu4(PO4)2O . X-ray investigations show square planar CuO4 polygons, twisted tetragonal CuO5 pyramids, CuO5 bipyramids and elongated (Cu,Mg)O6 octahedra.
Über ein niedervalentes Titan-Wolframoxid: Ti0,54W0,46O2 / On a Low Valent Titanium Tungsten Oxide: Ti0,54W0.46O2
Authors: Peters E. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of Ti0.54W0.46O2 have been prepared by CO2-LASER techniques. This phase crystallizes with a non-distorted rutile structure, space group D14
4H-P42/mnm, a = 4.6862(4), c = 2.9039(3) Å, Z = 2. Split positions of the statistically distributed metal ions show the existence of W-W pair formation as reported for pure WO2.
Verteilung und Valenz der Kationen im Spinellsystem ZnFeGaO4-Fe2GaO4 / Distribution and Valence of the Cations in the Spinel System ZnFeGaO4-Fe2GaO4
Authors: Rabbani Sima , Riedel Erwin
Published: February 2015

For the spinel system Zn1-ϰFe-λGaϰ-λ(Fe1+λGa1-λ)O4 the index λ has been determined by X-ray measurements: λ = 0 in the region 0 ≤ ϰ ≤ 0,35; the increase of λ to 0,62 within 0,35 ≤ χ ≤ 1 is nearly linear. The distribution of Fe2+ and Fe3+ ions over the lattice sites has been derived from lattice constants and ionic distances, and also by Mössbauer spectroscopy. In the spinels with ϰ < 0,3 the tetrahedral sites are preferably occupied by Fe2+ ions, for x > 0,5 Fe3+ ions dominate. At ϰ = 0,4 the occupation of the lattice sites by iron ions is statistical, the high temperature Mössbauer spectrum shows a single line only. All spinels are n-type hopping conductors mainly conducting via the octahedral sites.
Einkristall-Röntgenstrukturanalyse von Ba3CeIVRu2
IVO9, Ba3LnIII,Ru2
IV/VO9 (Ln = Sm, Dy, Er) und Ba3Ti2,4Ru0,6O9 / Single Crystal X-Ray Analysis of Ba3CeIVRu2
IVO9, Ba3LnIII,Ru2
IV/VO9 (Ln = Sm, Dy, Er) and Ba3Ti2,4Ru0,6O9
Authors: Müller-Buschbaum Hk. , Mertens B.
Published: February 2015

Single crystals of (I) Ba3CeRu2O9, (II) Ba3SmRu2O9, (III) Ba3DyRu2O9, (IV) Ba3ErRu2O9 and (V) Ba3Ti2 4Ru0,6O9 have been prepared by high temperature solid state reactions. The compounds were examined by X-ray techniques. They crystallize with hexagonal symmetry, space group D4
6h-P63/mmc with (I): a = 5.8738(7), c = 14.585(4); (II): a = 5.9137(5), c = 14.651(2); (III): a = 5.8805(5), c = 14.506(1); (IV): a = 5.8737(9), c = 14.470(3); (V): a = 5.7265(6), c = 14.006(2) Å, Z = 2. The crystal structures belong to the 6 L-perovskite type. Calculations of the Coulomb terms of the lattice energy led to the valence states (I): CeIV/RuIV and (II)-(IV): LnIII,/RuIV/V. (V) shows a partial statistic distribution of TiIV and RuIV.
Zwei Beispiele fiir partielle und totale Defekte im Ba▪Ln2Mo4O16-Typ: BaCu0,41▪0,59Pr2Mo4O16 und Ba▪Yb2Mo4O16 / Two Examples of Partial and Total Defects in the Ba▪Ln2Mo4O16-Typ: BaCu0,41▪0,59Pr2Mo4O16 and Ba▪Yb2Mo4O16
Authors: Gallinat St. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of (I) BaCu0,41Pr2Mo4O16 and (II) BaYb2Mo4O16 have been prepared by flux technique. Both compounds crystallize with monoclinic symmetry, space group C6
2h-C2/c with (I): a = 5.352(11), b = 12.888(2), c = 19.399(4) Å; β = 90.89(3)°; (II): a = 5.181(7), b = 12.467(3), c -19.350(3) Å , β -91.93(2)°, Z = 4. The crystal structure is characterized by 1
∞[BaMO12]-chains along [010]. In the first case the M positions are occupied by copper by about 41%, in the second case these positions remain completely unoccupied. With respect to the crystal chemistry of the reference compound Ba(Cu0.22Mg0,78)Nd2Mo4O16 all substances of the composition BaLn2Mo4O16 should be written as Ba▪Ln2Mo4O16 indicating the holes in the 1
∞[BaMO12]-chains by ▪.
Beiträge zur Chemie des Phosphors, 238 [1]. Synthese und Eigenschaften des Phosphinocyclotriphosphans (t-BuP)2P–P(SnMe3)2 / Contributions to the Chemistry of Phosphorus, 238 [1]. Synthesis and Properties of the Phosphinocyclotriphosphane (t-BuP)2P–P(SnMe3)2
Authors: Bäudler Marianne , Riese-Meyer Loert de
Published: February 2015

The new phosphinocyclotriphosphane (t-BuP)2P-P(SnMe3)2 (1) has been obtained by reaction of di-tert-butylchlorocyclotriphosphane with tris(trimethylstannyl)phosphane, and has been isolated in pure form. The yellow solid is stable below 0 °C under inert conditions. Compound 1 is a dynamic molecule, as the P atom of the [bis(trimethylstannyl)phosphino] group has a very low barrier to inversion due to the bulky and electropositive Me3Sn substituents.
Monomere Iodide von o-substituierten Aryl-Gallium- und Indiumverbindungen / Monomeric Iodides of o-Substituted Aryl Gallium and Indium Compounds
Authors: Meller Anton , Kümmel Christoph , Noltemeyer Mathias
Published: February 2015

Monomerie diiodides of 2,4,6-tri(tert-butyl)phenyl = (s-Mes), 2,4,6-triisopropylphenyl = (Trip)-and 2,4-di-tert-butyl-6-methylphenyl = (DBMP)-gallium and -indium were prepared by the reaction of the lithiated aryls with MI3 (M = Ga, In) in hexane/Et2O. s-MesInI2 (1), s-Mes2InI (2), s-MesGaI2 (3), s-Mes2GaI (4), Trip2InI (5) and (DBMP)2InI (6) were obtained and characterized by their mass and NMR spectra (1H, 13C), and/or by elemental analyses. An X-ray crystal structure analysis was carried out for 1.
Binding of Cations to 4f Metal Ions : Preparation and Properties of Lanthanide(III) Complexes Containing the Phenelzinium(1+) Cation as a Ligand
Authors: Lalioti Nickolia , Tsangaris John M. , Zafiropoulos Th. F. , Perlepes Spyros P.
Published: February 2015

Treatment of Ln2(SO4)3·nH2O (Ln = La, Ce, Pr, Nd, Sm. Eu, Gd ; n = 8, 9) with phenelzine dihydrogen sulfate, (phzH2) SO4, in 1N H2SO4 yields polymeric complexes with the general formula [Ln(SO4)2(H2O)2(phzH)], which contain the phzH+ cation as a ligand. The compounds have been characterized by elem ental analyses, X-ray powder patterns, thermal methods, magnetic susceptibilities and spectroscopic (IR, Raman, electronic diffuse reflectance and solid-state emission f-f spectra) studies. The prepared complexes most probably consist of 7-coordinated units, formed by four bridging bidentate sulfato groups, two terminal aqua molecules and one cationic phzH+ ligand.
Das Te4
2+-Polykation in den Strukturen von Te4(NbCl6)2, Te4(TaCl6)2, Te4(TaBr6)2 und Te4(Ta2OBr10) / The Te4
2+ Polycation in the Structures of Te4(NbCl6)2, Te4(TaCl6)2, Te4(TaBr6)2 and Te4(Ta2OBr10)
Authors: Beck Johannes , Bock Gunter
Published: February 2015

The reactions of Te, TeCl4 and MCl5 (M = Nb, Ta) in a sealed evacuated ampoule at 170 °C yield Te4(NbCl6)2 and Te4(TaCl6)2 as black, moisture sensitive crystals. Te4(TaBr6)2 is obtained from Te2Br and TaBr3 at 175 °C, and Te4(Ta2OBr10) is obtained in small yields as byproduct. The crystal structure determinations (all triclinic, P1, lattice constants for Te4(NbCl6)2: a = 654,2 pm, b = 673,9 pm, c = 1200,3 pm, α = 94,54°, β = 97,59°, γ = 85,29°, V = 521,5 -106 pm3, Z = 1; for Te4(TaCl6)2: a = 651,2(5) pm, b = 747,2(7) pm, c = 1107(1) pm, a = 100,33(8)°, β = 102,29(8)°, y = 89,24(8)°, V = 517,4 -106 pm3, Z = 1; for Te4(TaBr6)2: a = 680,9(3) pm. b = 710,4(3) pm, c = 1239,9(5) pm, α = 95,29(4)°, β = 98,05(4)°, γ = 85,31(4)°, V = 589,8 -106 pm3, Z = 1; for Te4(Ta2OBr10): a = 692,2(5) pm, b = 877,2(7) pm. c = 917(1) pm, α = 81,91(9)°, β = 86,39(9)°, γ = 74.23(6)°, V= 530,3-106 pm3, Z = 1) have shown, that all compounds contain nearly square planar Te4
2+ ions. Te4(TaCl6)2 and Te4(TaBr6)2 have distorted octahedral TaCl6- and TaBr6- ions. Te4(NbCl6)2 is isostructural to Te4(TaBr6)2 as was shown by the coincident lattice constants. Te4(Ta2OBr10) is isomorphous to Te4(Nb2OCl10) and contains a Ta2OBr10
2- ion in the form of two edge-sharing octahedra with the O atom in the centre of a linear Ta=O=Ta bridge. All structures adopt simple structure types. The arrangement of the ions in the compounds Te4(MX6)2 (M = Nb, Ta, W; X = Cl. Br) corresponds to the CdI2 structure type, and in Te4(Ta2OBr10) to the CsCl structure type. An analysis of the Te···Te bond length in Te4
2+ and the distance of Te···X (X = Cl, Br) contacts to the nearest neighbour halide anions in several Te4
2+-halometallates shows a clear correlation. Shortening of the Te···X contacts elongates the Te-Te bonds by a donor interaction of the halide ions with Te-Te-σ* orbitals.
Über verbesserte Darstellungsmethoden für CF3OCH3 / Improved Methods to Prepare CF3OCH3
Authors: Minkwitz Rolf , Konikowski Detlef
Published: February 2015

The reaction of CH3I with CF3OCl at 203 K yields CF3OCH3. The preparation of the ether by methylation of CsOCF3 with (CH3)2SO4 is also described.
Crystal Structure of Bis(3-Diethylamino-5-phenyl-1,2,4-dithiazolium) Hexachlorodicuprate, (dpd)2Cu2Cl6, at 120 K.
Authors: Fernández Vicente , Hartung Jürgen , Beyer Lothar , Kivikoski Jussi , Howard Judith A. K.
Published: February 2015

The crystal structure of the compound (dpd)2Cu2Cl6 at 120 K has been determined. Space group P21 /n , Z = 2, 3997 collected reflections, R = 6.8. Lattice dimensions (120(1)K) : a = 7.328 (8), b = 16.863 (14), c = 13.271 (10) Ä; β = 91.44(7).