bluuebunny/crossref_metadata_2025 huggingface dataset:
Kobaltinduzierte Synthese von Indolen aus Alkinen und Diaryldiazenen/Cobalt Assisted Synthesis of Indoles from Alkynes and Diaryldiazenes
Authors: Gstach H. , Kisch H.
Published: February 2015

Co(Cl)(PPh3)3 induces formation of 1/1 adducts (indoles) from alkynes and diaryldiazenes while Co(N2)(PPh3)3 gives rise to 2/1 adducts, respectively.
Notizen:Die Kristallstruktur von polymerem Bis (dimethyl- glyoximato) -pyrazin - eisen(II)a/Crystal Structure of Polymerie Bis(dimethylglyoximato)pyrazine Iron (II)a
Authors: Kubel Frank , Strähle Joachim
Published: February 2015

Bis(dimethylglyoximato)pyrazine-iron(II), (dmgH)2Fepyz, crystallizes isotypicly with the Co(II) compound (dmgH)2Copyz in the space group C2/m, the lattice constants being a = 1407, b = 680.0, c = 919 pm, β=125.6°, Z = 2. The structure was determined using the powder pattern. It shows planar (dmgH)2Fe moieties which are polymerized via axially bonded, bridging pyrazine ligands to form a linear chain of symmetry 2/m. The distance Fe-N = 200 pm in the chain is considerably shorter than in (dmgH)2Copyz (Co-N = 224 pm), since the latter has one extra electron in an antibonding orbital.
Synthesis and Characterisation of an [18]Crown-5-Ligand and its NaNCS Complex
Authors: Itter Franz-Albert von , Vögtle Fritz , Weber Gabriela , Sheldrick George M.
Published: February 2015

The new [18]crown-5 ligand -[18] ⟨O5-(2,2′)-diphenylmethano·24 -coronand-5⟩ [1] -, containing a benzylic CH2 group, was prepared by condensation of 2,2'-dihydroxydiphenylmethane with tetraethylene glycol dichloride. The ligand exhibits an endo-conformation and short O···H2C contacts. The macrocycle ligates Na+ by contracting its cavity so that its five O atoms form an approximately regular pentagon.
Atran-analoge Verbindungen des Typs / Atrane Analogous Compounds of Type
Authors: Grobe Joseph , Voulgarakis Nikolaos
Published: February 2015

Heterocyclic ring compounds of type I (compounds 9 and 10) have been prepared by condensation reactions of α,ω-difunctional derivatives XMe2SiCH2M'Me2X (X = Cl, NMe2; M' - Si, Sn) with N-methyldiethanolamine using the "Dilution Principle". The starting compounds XMe2SiCH2M'Me2X are obtained by reacting XMe2SiCH2MgCl with ClM'Me2X (Scheme, Abb. 1). The existence of transanular N→Si or N→M' interactions depends on the N-M distance and the acidity of the acceptor atoms. In order to clarify the weight of these factors acyclic analoga of compounds 9 and 10 have been prepared.
Triphenylstannyltris(trimethylphosphan)cobalt - Molekülstruktur und Eigenschaften / Triphenylstannyltris(trimethylphosphane)cobalt -Molecular Structure and Properties
Authors: Klein Hans-Friedrich , Ellrich Klaus , Neugebauer Dietmar , Orama Olli , Krüger Karl
Published: February 2015

Potassium cobaltates K+CoLsL' -(L = Me3P, L' = N2, olefin) react with SnCl(C6H5)3 or GeBr(CeH5)3 to give tetracoordinate complexes containing Co-Sn and Co-Ge bonds. Crystal and molecular structures of two single crystals were determined. They show tetrahedral molecules Co[Sn(C6H5)3][P(CH3)3]3 in different packing order. Both tetra-coordinate compounds take up small ligands thereby completing their 18-electron valence shells in compounds Co[E(C6H5)3]L3L' (L = (CH3)3P; E = Ge, L' = CO; E = Sn, L' = CO, C2H4). A sparingly soluble paramagnetic adduct Co[Sn(C6H5)3]L4 is believed to contain a tin-bonded phosphane.
Die quaternären Systeme ZnAl2S4-ZnGa2S4, ZnAl2S4-CdAl2S4 und ZnAl2S4-ZnAl2Se4. Röntgenographische und schwingungsspektroskopisehe Untersuchungen / Investigation of the Quaternary Systems ZnAl2S4-ZnGa2S4, ZnAl2S4-CdAl2S4 and ZnAl2S4-ZnAl2Se4 by X-Ray Diffraction and Vibrational Spectroscopy
Authors: Haeuseler H. , Cansiz A.
Published: February 2015

The quasi-binary systems Zn1-xCdxAl2S4, ZnAl2(1-x)Ga2xS4 and ZnAl2S4(1-x)Se4x have been investigated by X-ray diffraction and vibrational spectroscopy. In the spinel ZnAI2S4 up to 20% of Zn can be replaced by Cd. In the two other systems, ZnAl2S4 has no detectable homogeneity range. The thiogallate phases have much broader ranges of homogeneity. The compositions of the compounds at the phase boundary of the thiogallate phase are Zn0.4Cd0.6Al2S4, ZnGa0.4Al1.6S4, and ZnAl2S2.8Se1.2. At approximately 950 °C ZnAl2Se4 undergoes a reversible phase transition to a wurtzite-type structure. This phase transition is also observed for the solid solutions ZnAl2S4(1-x)Se4x; with 1.0 > x > 0.3. The FIR spectra are discussed.
[1]Metallocenophane: 1H-NMR-Untersuchungen / [1]Metallocenophanes: 1H NMR Investigations
Authors: Köpf Hartmut , Klouras Nikolaos
Published: February 2015

The synthesis of a series of [1]metallocenophanes has been achieved. The structure and conformation of these compounds are discussed in the light of their 1H NMR spectra.
Schwefel-Stickstoff-Verbindungen, XII [1]. 19F-NMR-und 13C-NMR-spektroskopische Untersuchung einiger aromatisch substituierter Schwefeldiimide / Sulfur-Nitrogen Compounds, XII [1]. 19F NMR and 13C NMR Spectroscopic Investigation of Some Aromatic Substituted Sulfurdiimides
Authors: Brands Gilbert , Golloch Alfred
Published: February 2015

19F NMR and 13C NMR spectra of the sulfur(IV)diimines R1-NSN-R2 (R1/2 = C6H5, C6F5, C6H5S, C6F5S) and the corresponding N-sulfinylamines R1/2 -NSO are discussed. Chemical shifts are correlated to the electron withdrawing properties of the substituents.
Darstellung und Kristallstruktur des 2:3-Adduktes von Antimontrichlorid und 4-Phenylpyridin, 2 SbCl3 · 3 (C11H9N) / Preparation and Crystal Structure of the 2:3 Adduct of Antimony Trichloride and 4-Phenylpyridine, SbCl3 · 3 (C11H9N)
Authors: Lipka Annegret
Published: February 2015

A congruently melting phase of molar ratio 2:3 was identified in the system SbCl3/4-phenylpyridine. The structure consists of two different types of complex units: One SbCl3 molecule is bonded to one 4-phenylpyridine ligand only, whereas the other one forms a complex with two 4-phenylpyridine ligands. The SbCl3 unit in the 1:1 species is pyramidally shaped, whereas the SbCl3 unit in the 1:2 species displays a T-shaped geometry. The mean angle between the phenyl and pyridyl planes is 33.3°; mean bond lengths are 〈Sb-Cl〉 = 247.6 pm and 〈Sb-N〉 = 241.7 pm.
Zur Darstellung und Struktur des 1.3-Dichloro-5-N.N-dimethylamino-1.3-dithia-2.4.6-triazins / Synthesis and Structure of 1,3-Dichloro-5-N,N-dimethylamino-1,3-dithia-2,4,6-triazine
Authors: Roesky Herbert W. , Schäfer Pierre , Noltemeyer Mathias , Sheldrick George M.
Published: February 2015

The six membered ring of composition (CH3)2NCN3S2Cl2 3 a was prepared from N,N-dimethylguanidinhydrochloride and trithiadiazindichloride. 3 a was characterized on the basis of mass, 1H, 13C NMR spectra and X-ray structure analysis. Crystals of 3 a are monoclinic, space group P21/c, with a = 660.3(6), b = 834.5(7), c = 1774.7(15) pm, β = 112.83(6)° and Z = 4. The C2N unit lies approximately in the plane of the [-CNSNSN-] ring, with both Cl atoms on the same side of the ring.
Diphenylphosphino -α -aminosäureester als Liganden in Palladium(II)-und Platin(II)-Komplexen [1] / Diphenylphosphino-α-Amino Acid Esters as Ligands in Palladium(II) and Platinum(II) Complexes [1]
Authors: Trampisch Herbert , Beck Wolfgang
Published: February 2015

cis-Dichlorobis(chlorodiphenylphosphine)palladium-and platinum(II) react with N-alkyl-α-amino acid esters to give the complexes MCl2[Ph2PN(R)C(H)(R')CO2Me]2 (M = Pd, Pt; R = CH2Ph, i-C3H7; R' = CH3, CH2Ph). With lysine ester dimeric, bis(chelate) complexes

(M = Pd, Pt; R = CH3, C2H5)

have been isolated. The reaction of cis-MCl2(PPh2Cl)2 with cysteine and serine methylester affords the complexes MCl2[Ph2P(X)CH2C(H)(NH2)CO2CH3]2 (M = Pd, Pt; X = O, S).
Zur Struktur von (Pyrazolinonyl)-(hydroxypyrazolylium)methanperchloraten NMR-, IR-spektroskopische Studien und Kristallstruktur / The Structure of (Pyrazohnonyl)-(hydroxypyrazolyhum)methaneperchlorates NMR, IR Spectroscopic Studies and Crystal Structure
Authors: Burschka Christian , Akgün Eyup , Pindur Ulf
Published: February 2015

The structures of 1a-1d were investigated by spectroscopic methods and in the case of la in addition by X-ray diffraction, 1a, vicarious for the compounds 1, is stabilized in solution and in the crystal by an intramolecular hydrogen bond in an eight-membered ring. The IR and NMR spectra show that 1 exhibit a symmetrical structure. In the case of 1 a the molecular structure is affected by unsymmetrical packing and electrostatic effects in the crystal and is therefore approximated best between the forms I and II.
Lösliche Phthalocyaninatometalloxane, Dotierung und Leitfähigkeit / Soluble Phthalocyaninatometaloxanes, Doping and Conductivity
Authors: Metz Josef , Pawlowski Georg , Hanack Michael
Published: February 2015

The polymeric μ-oxo-(tetraalkylphthalocyaninato)-metal IV B derivatives 1 a-d were synthesized by thermal condensation of the monomeric dihydroxo(tetraalkylphthalo-cyaninato)-metal IV B compounds 5 a-d. The high solubility of the metaloxanes 1 a-d enables a homogeneous reaction with the dopant. The electrical conductivities of the undoped and doped compounds are reported.
Derivate des Benzo[1.3]dioxols, 47 [1]. Darstellung und Reaktionen des 4.8-Dimethoxy-bis[1.3]dioxolo[4.5]benzo- [1.2-d; 1′ .2′ -f] [1.3]dioxepins / Derivatives of 1,3-Benzodioxoles, 47 [1]. Preparation and Reactions of 4,8-Dimethoxy-bis[1,3]dioxolo[4,5]benzo- [1,2-d; 1',2'-f][1,3]dioxepine
Authors: Dallacker Franz , Coerver Wim
Published: February 2015

In 1957 some dibenzo[d,f][1,3]dioxepines were isolated from Cercospora kikuchii. We describe the preparation of 4,8-dimethoxy-bis[1,3]dioxolo[4,5]benzo[1,2-d; 1',2'-f][1,3]-dioxepine (3). It shows a high SE-reactivity. Bromination yields the monobromo-and dibromocompounds 3 a and 3 b. Treatment of 3 with copper(II) nitrate leads to the dinitrocompound 3c. With the same reagent 3a gives 3d. Reduction of 3d with hydrogen and Palladium as catalyst yields the mono-amine 3e under bromine loss. Under the same reduction conditions in acetic anhydride 3d and 3c yields 3f respectively 3g.

The carboxylic acid 3i and the aldehyd 3h are prepared by bromine-lithium exchange from 3 a. In the same manner the dibromocompound 3 b is a suitable starting material to obtain the dicarboxylic acid 3k and the dialdehyd 3j. 3j undergoes easily a thiazolium catalysed oin-condensation, yielding the phenanthrenequinone 3l. The cyclic anhydride 3 m can be prepared by heating 3 k in acetic anhydride.
Direkte Lithiierung von BicycIo[3,2,1]octa-2.6-dien / Direct Lithiation of Bicyclo[3,2,1]octa-2,6-diene
Authors: Köhler Frank H. , Hertkorn Norbert
Published: February 2015

Bicyclo[3,2,1]octa-2,6-diene (1) has been lithiated directly with t-butyllithium/TMEDA at low temperature. After quenching with tri-methyltin chloride essentially two stannyl derivatives of 1 were obtained. The stannyl group did not bind to the allylic carbon of 1 as expected but to C-6 and C-7. This has been shown by means of elemental analysis, mass spectroscopy as well as 1H, 13C and 119 Sn NMR spectroscopy.
Über Darstellung und Eigenschaften von Na[η3 -C3H5Fe(NO)(CO)CN] und η3 -C3H5Fe(NO)(CO)CNMe/Synthesis and Properties of Na[η3-C3H5Fe(NO)(CO)CN] and η3 -C3H5Fe(NO)(CO)CNMe (η3 -C3H5 = Allyl)
Authors: Moll Matthias , Seibold Hans-Jürgen , Merbach Peter
Published: February 2015

The allyl iron complexes η3 -C3H5Fe(NO)(CO)L (L = CN-, CNMe) can be obtained by the reaction of η3 -C3H5Fe(NO)(CO)2 with NaN(SiMe3)2 and subsequent methylation.
Neuartige basische Liganden für die homogenkatalytische Homologisierung von Methanol zu Ethanol, I Synthese basischer, dreizähniger P-N-haltiger Chelatliganden und deren Verhalten gegenüber Carbonylverbindungen von Metallen der VI./Nebengruppe Novel Basic Ligands for the Homogeneous Catalytic Homologation of Methanol to Ethanol, I Synthesis of Basic Tridentate P-N Containing Chelate Ligands and their Behaviour Towards Carbonyl Compounds of Group VI Metals
Authors: Lindner Ekkehard , Rauleder Hartwig , Hiller Wolfgang
Published: February 2015

The novel, strongly basic, tridentate P-N-ligands PhP(XC5H4N)2 l a - c [X = CH2 (a), O (b), NH (c)] are obtained between -60 and 0 °C by the action of PhPCl2 on 2-picolyllithium, 2-hydroxy- and 2-aminopyridine, respectively, using NEt3 and 2-aminopyridine as auxiliary bases, l a - c react with (OC)3M(NCCH3)3 to give the tricarbonyl-P-N-ligand complexes (OC)3M[PhP(XC5H4N)2] 2 - 4 a - c [M = Cr (2), Mo (3), W (4)]. 4c crystallizes in the monoclinic space group P2i/n with Z = 4 and contains two five-membered, slightly distorted chelate rings.
Verfeinerung der Kristallstruktur von Tripalladium-di-tetrathiophospliat Pd3(PS4)2 Refinement of the Crystal Structure of Tripalladium-di-tetrathiophosphate Pda3(PS4)2
Authors: Simon Arndt , Peters Karl , Hahn Harry
Published: February 2015

The structure of the title compound has been determined by X-ray crystallography. The title compound is synthesized from the elements at 600 °C. Its crystal structure, derived from powder data [3] is refined by single crystal diffractometer data. The structure is trigonal (P3̅ml, α = 684.1(1), c = 724.4(1) pm); Pd2+ cations and PS4
3- anions form a network with an anti-Claudetite (AS2O3) type structure. The PS4 units are distinctly distorted from ideal tetrahedral symmetry. The Pd atoms have a planar environment of 4 S atoms.
Umsetzungen von Monomethylthalliumdiacetat mit Aminen/Reactions of Monomethylthallium Diacetate and Amines
Authors: Knips Ulrich , Huber Friedo
Published: February 2015

Decomposition of MeTl(OAc)2 (Me = CH3, HO Ac = CH3COOH) in methanol in the presence of amines, like 2-, 3- and 4-picoline, benzylamines, dimethylaniline causes mainly N-methylation; the concurring O-methylation of acetate, giving MeOAc, is only of minor importance. The rate of N-methylation increases in the series 2-picoline ≤ pyridine < 3- picoline < 4-picoline ≤ dimethylaniline ≤ dimethylbenzylamine. Picolinic acid and MeTl(OAc)2 (molar ratio 1:1) react to give 25% N-methylpicolinic acid and 75% MeOAc; when the molar ratio was at least 2:1, a 1:1 mixture of N-methylpicolinic acid and the methylester of picolinic acid was produced. These results and rate changes in different solvents are explained by assuming MeT10Ac+ being the active methylthallium electrophile.
Synthesis, IR Spectrum and Crystal Structure of a,a′-Dipyridyldi(iodineazide)/Synthesis, IR Spectrum and Crystal Structure of a,a′-Dipyridyldi(iodineazide)
Authors: Dörner Hans , Dehnicke Kurt , Dehnicke Kurt , Massa Werner , Schmidt Roland
Published: February 2015

The complex [a,a′-dipyridyl(IN3)2] can be prepared by reaction of a,a′-dipyridyl with iodine azide in CH2CI2 solution. It forms stable, yellow, moisture-sensitive crystals of melting point 73 °C. According to the IR spectrum the IN3 molecules are covalently bonded to the N atoms of the dipyridyl via the iodine atoms. The crystal structure determination was carried out by X-ray methods (2127 independent reflexions, R = 3.2%). The complex crystallizes in the space group P21/c with four formula units per unit cell, (a = 1299, b = 726, c -1647 pm; β = 96.1°). The IN3 molecules form linear bridges Nα-I-N to the nitrogen atoms of the pyridyl rings with bond lengths Nα-I 217 pm and Npyr-I 244 pm. The dihedral angle of the pyridyl rings is 63.4°.
Carbonylniobium Chemistry, IV Derivatives of η5 -C5H5Nb(CO)4 with Tridentate Phosphines
Authors: Hoch Martin , Rehder Dieter
Published: February 2015

The photo-induced reaction between CpNb(CO)4 and Ph2P(CH2)2PR(CH2)2PPh2 (L; R = Ph, Cy) yields the chelated five-membered ring complexes cis-[CpNb(CO)2L] (two isomers in the case of R = Cy). The uncordinated PPh2 group reacts with CpNb(CO)3THF to form CpNb(CO)2(μ-L)CpNb(CO)3. IR, 31P and 93Nb NMR spectra are discussed and compared with corresponding data of the analogous vanadium complexes.
Dithiocarbonate and Trithiocarbonate Complexes of Palladium(II); Crystal Structure of Pd(Ph3P)2(CS2O)· CH2Cl2
Authors: Jones Peter G. , Sheldrick George M. , Usón Rafael , Forniés Juan , Usón Miguel A.
Published: February 2015

Di-and trithiocarbonate complexes of palladium(II) have been prepared by the action of O2 or S8 on PdL2(η2 -CS2) in the presence of excess L (L = phosphine ligand). 31P NMR data for Pd(PPh3)2(CS2O) are consistent with the presence in solution of both S̱,S̱ and S̱,O̱ coordinated dithiocarbonate. An X-ray crystal structure of the dichloromethane solvate [P1̄, a = 1103.6(4), b = 1343.4(5), c = 1368.5(5) pm, α = 94.77(3), β = 94.67(3), γ = 113.64(3)°, Z = 2, R = 0.059] suggests that an equivalent disorder may occur in the solid state.
Darstellung und Reaktionen von bicyclischen Verbindungen mit einer Phosphor-Phosphor-Bindung/Preparation and Reactions of Bicyclic Compounds with a Phosphorus-Phosphorus-Bond
Authors: Roesky H. W. , Amirzadeh-Asl D.
Published: February 2015

The reaction of N,N′-dimethyl-N,N′-bis(trimethylsilyl)urea with PCl3 leads to the bicyclic compound OP2[MeNCONMe]2 (3) with a direct phosphorus-phosphorus bond and to the bicycle MeNP2[MeNCONMe]2 (4). 3 reacts with tetrachloro-o-benzoquinone (TOB) to yield the spirocycle Ce6Cl4tMeNCONMe]2P2O (5) with a λ4P-λ5P-bond. The Lewis acids SbCl5 and SnCL4 react with 3 to give the adducts 6 and 7. The reactions of 3 with the metal carbonyls Fe2(CO)9, Cr(CO)5THF and Cr(CO)4C7H8 lead to the metal complexes 8-10. The compounds were characterized on the basis of 31P NMR and mass spectra.
The Chemistry of Heteroarylphosphorus Compounds, Part 16.+ An X-Ray Structural Study of (2-Thienyl)bis(2,2′-biphenylylene)phosphorane. A Comparison with Related Methyl and Aryl bis(2,2′-biphenylylene)- spirophosphoranes
Authors: Allen David W. , March Lorraine A. , Nowell Ian W. , Tebby John C.
Published: February 2015

Crystals of the title compound are monoclinic, a= 18.9 93 (11), b = 8.757(5), c= 13.267(8) Å, β = 106.60(5)°, Z = 4 in space group Cc (Cs
4 , No. 9). The structure was determined by Patterson and electron-density methods and refined by least squares techniques to R= 0.081, R′ = 0.085 for 1293 independent reflections classified as observed. The molecule is found to adopt an almost regular trigonal bipyramidal geometry in which the two biphenylylene units span apical-equatorial positions and the 2-thienyl group occupies the remaining equatorial site. The 2-thienyl group, which is disordered, does not lie in the equatorial plane, and there is no indication of C2pπ → P3dπ-t interactions between the heteroaryl group and phosphorus. The steric requirements of the 2-thienyl group appear to be comparable with those of methyl and phenyl groups in bis(2,2′-biphenylylene)spiro-phosphoranes.
Notizen: Zum Verständnis der zentralen Rolle des Schwefels in Multi-Metall-Aggregaten mit verschiedener Elektronenpopulation: [S2WS2CoS2WS2]n- (n = 2, 3)/On the Central Role of Sulfur in Multi Metal Aggregates with Different Electron Populations: [S2WS2CoS2WS2]n-(n = 2, 3)
Authors: Müller Achim , Hellmann Winfried , Schimanski Uwe , Jostes Rainer , Newton William E.
Published: February 2015

The hetero metal sulfur aggregates [Co(WS4)2] n- (with variable electron population: n = 2, 3) could be isolated as salts and characterized by physical measurements (in-cluding X-ray structure analysis). Experimental and theoretical investigations show that due to a strong metal → ligand electron delocalisation WS42-(like MOS4
2-) is a non-innocent ligand and that the additional charge upon reduction is located mainly at the S atoms of the ligand system.
Notizen: The Reaction of Aniline with Isopropylidene-D-glyceraldehyde
Authors: Angrick Michael
Published: February 2015

The reaction of aniline with 2,3-O-isopropyldene-D-glyceraldehyde supplies the dimeric form of the expected Schiff's base which may serve as a model for the initial step of the Maillard reaction.
A New Synthesis of β-Carbolines
Authors: Atta-ur-Rahman  , Sultana Mumtaz
Published: February 2015

A new one step synthesis of β-carbolines is described, which involves the direct conversion of N-imidotryptamines to the corresponding lactams on reaction with P2S5.
Beiträge zur Chemie des Phosphors, 126. Tris(tert-butylphosphino)-phosphan, P(t-BuPH)3 - ein teilsubstituiertes Derivat von iso-P4H6/ Contributions to the Chemistry of Phosphorus, 126. Tris(tert - butylphosphino)phosphane, P(t-BuPH)3 - a Partially Substituted Derivative of iso-P4H6
Authors: Baudler Marianne , Hellmann Jochen , Schmidt Thomas
Published: February 2015

The reaction of tris(bromo-tert-butylphosphino)phosphane, P(t-BuPBr)3, with lithium aluminium hydride leads to the title compound P(t-BuPH)3 (1), which could be isolated in a pure state. 1 is the first partially substituted derivative of iso-tetraphosphane(6), P(PH2)3, and was characterized in all details. Because of the chirality of the Z-BuPHgroups, 1 forms two diastereomers with RRS(SSR)- and RRR(SSS)-configuration in a ratio of about 3:1. The conformation of both isomers, which could be deduced from the 31P NMR parameters, is mainly determined by the steric situation of the molecule.
Barrier to Rotation about Sulfur-Sulfur Bonds in Homocyclic Sulfur Molecules
Authors: Steudel Ralf
Published: February 2015

It is shown that the distances (d) of the 19 longest bonds in 9 homocyclic sulfur rings of type Sn (n = 6-20) depend on the torsional angles (τ) which vary between 0° and 140°. The function d = f(τ) is smallest for τ = 90-100° and largest for τ = 0°; the corresponding bond distance variation amounts to 13 pm or 6%. The height of the torsional cis-barrier is estimated from the enthalpy of formation of gaseous S7 as equal to or smaller than 24 kJ/mol.
Cycloaddition von Schwefelkohlenstoff an die Azidliganden in (Ph3P)2Pd(N3)2 und [Co(N3)4]2–/ Cycloaddition of Carbon Disulfide to the Azide Ligands of (Ph3P)2Pd(N3)2 and [Co(N3)4]2-
Authors: Peter Wolf Peter , Beck Wolfgang
Published: February 2015

(Ph3P)2Pd(N3)2 reacts with CS2 by 1,3-dipolar cycloaddition to give the thiatriazoline- 5-thionato complex (Ph3P)2Pd(N3CS2)2. From the reaction of [Ph4As]2[Co(N3)4] with CS2, the isotliiocyanato complex [Ph4As]2[Co(NCS)4] has been isolated, and the intermediate thiatriazoline-5-thionato complex [Ph4As]2[Co(N3CS2)4] could be detected by its electronic spectrum.
Über neue monocyclische Acyloxyfluoroborane 2.2.6.6-Tetrafluoro-1.4-dialkyl-1.3.5-trioxa-1.6-diboracyclohexene: Darstellung, Molekül- und Kristallstruktur/ New Monocyclic Acyloxyfluoroboranes 2,2,6,6-Tetrafluoro-1,4-dialkyl-1,3,5-trioxa-2,6-diboracyclohexenes: Synthesis, Molecular and Crystal Structure
Authors: Binder Herbert , Matheis Walter , Deiseroth Hans-Jörg , Fu-Son Han
Published: February 2015

Acyloxyfluoroboranes Trimeric alkoxydifluoroboranes (F2BOR)3 (2) react with organic acid anhydrides by substitution of a ring group OR forming monocyclic acyloxyfluoroboranes of the type 2,2,6,6-tetrafluoro-l,4-dialkyl-l,3,5-trioxa-2,6-diboracyclohexene (3). The X-ray crystal structure determination of 3a shows two conformational isomers: two planar and two non-planar six-membered rings are present in the unit cell. The ring conformation is influenced by weak intermolecular H — F interactions.
β-NbBr5, eine neue Modifikation von Niobpentabromid mit einer eindimensionalen Lagenfehlordnung/ β-NbBr5, a New Modification of Niobium Pentabromide Having One-Dimensional Stacking Disorder
Authors: Müller Ulrich , Klingelhöfer Paul
Published: February 2015

While trying to react NbBr5 with sulfur in a closed tube, crystals of the new modification β-NbBr5 were obtained. Its X-ray diffraction patterns have sharp reflexions and diffuse streaks showing the presence of a one-dimensional disorder. From the sharp reflexions alone, a statistically averaged sub-structure results; it has the space group Ccmm and the lattice constants a0 = 644, b0 = 1867 and c0 = 615 pm. Taking into account the diffuse streaks, the true structure was deduced; its lattice constants are a = 2a0, c = Co, b indefinite due to the disorder. β-NbBr5 is isostructural to tantalum pentaiodide. It consists of layers of (NbBr5)2 molecules that are stacked with displacement faults in the direction of b. The bromine atoms have a hexagonal close-packing arrangement.
Transition Metal Complexes with Sulfur Ligands, IV. Synthesis and Reactions of Mo (IV) Complexes with the Tetradentate Thioether-thiol Ligand 2,3,8,9-Dibenzo-1,4,7,10-tetrathiadecane
Authors: Kaul Bharat B. , Sellmann D.
Published: February 2015

Synthesis and characterization of non-oxo Mo(IV) complexes with the tetradentate thioether-thiol ligand 2,3,8,9-dibenzo-1,4,7,10-tetrathiadecane(dttd-H2) are reported. MoCl4(THF)2 reacts with dttd-H2 in THF at room temperature to give the paramagnetic (2.61 BM, 295 K) [Mo(dttd)Cl2]. The chlorine ligands in [Mo(dttd)Cl2] can be substituted by sulfur ligands yielding diamagnetic complexes as [Mo(dttd)(CeH4S2)], [Mo(dttd)(SC2H4S)] and [Mo(dttd)(SC2H5)2]; with Na2S, NaHS or H2S, the di-μ-sulfido bridged complex [(dttd)Mo(S)2Mo(dttd)] is obtained. The reduction of [Mo(dttd)Cl2] by various reducing agents in the presence of CO or NO yields labile carbonyl and nitrosyl species in solution. In contrast to [Mo(dttd)Cl2], the complexes with MoSe cbromophores showed no reactivity to CO or NO under reducing conditions.
Zur Stereochemie von Diazadien-Metall-Komplexen, V. Molekülstrukturen und CO-Kraftkonstanten nicht-starrer Chrom-, Molybdänund Wolframcarbonylderivate DAD M(CO)3(*CO) (*C0 = 12CO, 13CO, C180)/ Stereochemistry of Diazadiene Metal Complexes, V Molecular Structures and CO Force Constants of Non-Rigid Chromium, Molybdenum and Tungsten Carbonyl Derivatives DAD M(CO)3(*CO) (*CO = 12CO, 13CO, C18O)
Authors: Dieck Heindirk tom , Mack Thomas , Peters Karl , Schnering Hans-Georg von
Published: February 2015

Diazadiene metal tetracarbonyls, DAD M(CO)4, (M = Cr, Mo, W; DAD = R-N = CH-CH = NR with aliphatic and aromatic substituents R) show equidistribution of one labelled CO when synthesized from fac-DAD M(CO)3(CH3CN) as a consequence of intramolecular CO site exchange. The structures of two Mo-complexes (1: R = iso-propyl; 2: R = 2,6-diisopropylphenyl) with DAD's of different bulkiness have been solved by X-ray methods. From the infrared solution spectra, including those of isotopically labelled (13CO, C18O) compounds, all of the force constants k1, k2, ktt, kcc and kcc have been calculated independently. The ratios of interaction force constants deviate sharply from Cotton-Kraihanzel assumptions, perhaps because of the substantial deviation of the iraws-pair of CO groups from linearity (1: 154.5°, 2: 147.9°). The solid state N-Mo, Mo-C and C - O bond lengths are neither in agreement with the generally accepted picture for donor/acceptor influences nor with typical IR data and force constant interpretations. (2 with higher v(CO) and k1, k2 has the longer CO bonds and shorter Mo-C bonds than 1.)

The force constant sets have been used to calculate CO frequencies for over 60 labelled compounds with good accuracy (Δv < 2 cm-1).
Übergangsmetall-Carben-Komplexe, CXXXI. Umsetzung von [(CO)5WCNEt2]BF4 mit anionischen Organylverbindungen von Elementen der V. Hauptgruppe/ Transition Metal Carbene Complexes, CXXXI. Reaction of [(CO)sWCNEt2]BF4 with Anionic Organyl Compounds of Group V Elements
Authors: Fischer Ernst Otto , Reitmeier Rudolf
Published: February 2015

The cationic carbyne complex [(CO)5WCNEt2]BF4 (1) reacts with potassiumdiphenylamide, KNPh2, with nucleophilic addition of the amide anion to give (CO)5W[C(NEt2)NPh2] (2). The corresponding reactions with KPPh2, KPEt2, KPMePh, NaSbPh2 and NaBiPh2 yield the complex [(CO)5W(CNEt2)]2 (3), which is formed by reductive dimerization of two carbyne fragments. In case of KPMePh the carbene complexes (CO)5W[C(NEt2)PMePh (4) and trans-(MePhPH)(CO)4W[C(NEt2)PMePh] (5) are also obtained. On warming in solution 5 spontaneously rearranges to the novel cyclic carbene complex

(6). Reaction conditions, properties and spectroscopic data of the new compounds are reported.
Übergangsmetall-Carbin-Komplexe, LXXIY. Synthese thermisch stabiler neutraler Carbin-Carbonyl-Komplexe von Chrom, Molybdän und Wolfram mit den zweizähnigen Liganden 2.2′ -Bipyridyl und 1.10-Phenanthrolin/ Transition Metal Carbyne Complexes, LXXIV. Synthesis of Thermostable Neutral Carbyne Carbonyl Complexes of Chromium, Molybdenum, and Tungsten with the Bidentate Ligands 2,2′-Bipyridyl and 1,10-Phenanthroline
Authors: Filippou Alexander , Fischer Ernst Otto
Published: February 2015

Reaction of trans-bromotetracarbonyl(phenylcarbyne)-complexes of chromium, molybdenum and tungsten and trans-bromotetracarbonyl(methylcarbyne) complexes of chromium and tungsten with the bidentate ligands 2,2′-bipyridyl and 1,10-phenanthroline results in the replacement of two carbonyl groups leading to very thermostable carbyne complexes with the general formula Br(CO)2LMCR (L: 2,2′-bipy, ophen; M: Cr, Mo, W; R : CH3, C6H5).
η3-Allylmetall-Schwefel-Komplexe, IV/ η3-Allyl-hydrogensulfidopalladium- und -platin-Komplexe/ η3-Allylmetal-Sulfur Complexes, IV. η3-Allyl-hydrogensulfidopalladium and -platinum Complexes
Authors: Bogdanović Borislav , Rubach Martin , Seevogel Klaus
Published: February 2015

Abstract η3-Allyl- or η3-methallyl-η5-cyclopentadienylpalladium react with hydrogensulfide at - 78 °C with selective cleavage of the cyclopentadienyl group to give the dimeric, thermolabile η3-allyl- or η3-methallylhydrogensulfidopalladium (2, 2a), which decompose above ≈ - 60 °C to palladiumsulfide and propene or isobutene. The new compounds have been characterised by 1H NMR, IR and Raman spectroscopy. Similarly, η3-allyl- and η3- methallylhydrogensulfidoplatinum (6, 6 a) have been prepared from hydrogensulfide and η3-allyl- and η3-methallyl-?75-cyclopentadienylplatinum, respectively. From bis(??3-allyl)- or bis(?y3-methallyl)palladium and H2S rj3-allyl- or ??3-methallylhydrogensulfidopalladium (2', 2a') have been obtained and their IR spectra and physical properties found to differ from those of 2 or 2a.
η3-Allylmetall-Schwefel-Komplexe, V. Mono- und bimetallische, mehrkernige η3-Allylmetall-Sehwefel-Komplexe des Nickels, Palladiums und Platins/ η3-Allylmetal-Sulfur Complexes, V. Mono- and Bimetallic, Polynuclear η3- Allylmetal-Sulfur Complexes of Nickel, Palladium and Platinum
Authors: Bogdanović Borislav , Göttsch Peter , Rubach Martin
Published: February 2015

η3-Allylhydrogensulfidopalladium (6) reacts with bis-(η3-allyl)- (4) or η5-cyclopentadienyl-η3-allyl-palladium (11) with elimination of propene to give the known η3-allylpalladium- sulfur-cluster (2). The same method was used to prepare the first bimetallic η3-allyl-Ni-Pd-, Ni-Pt- and Pd-Pt-sulfur complexes 12-14 (IR-spectra); their structures are still unknown. The polynuclear η3-methally Ipalladium- and -platinum-sulfur complexes 2 a and 3 a, soluble in benzene and toluene, have been prepared from the corresponding bis(η3-methallyl)metal compounds and H2S. In benzene, 2 a may have a structure in which the four palladium atoms adopt a square planar (2a′) or tetrahedral (2a″) geometry.
η3-Allylmeta]l-Schwefel-Komplexe, VI. Anionische η3-Allylnickel- und -palladium-Schwefel-Cluster/ η3-Allylmetal-Sulfur-Complexes, VI. Anionic η3-Allylnickel- and -palladium-Sulfur-Clusters
Authors: Benn Reinhard , Bogdanović Borislav , Göttsch Peter , Rubach Martin
Published: February 2015

η3-Allylhydrogensulfidonickel (2) reacts with n-butyllithium with elimination of lithium sulfide and formation of the ionic η3-allylnickel-sulfur-cluster [(η3-C3H5Ni)3S2]+[Li(THF)2]- (4). The crystal structure of the analogous THF-TMEDA-adduct (4′) indicates that the nickel and sulfur atoms of the anion adopt a trigonal bipyramidal arrangement, in which the sulfur atoms are at the apices of the bipyramid. The Li(THF)2+ cation in 4 can be replaced by the (n-C4H9)4N+ cation (5). The 1H NMR spectra suggest the presence of two stereoisomers of the anionic clusters in 4 and 5 having C3h and Cs symmetry. In the reaction of η3-allyl- or η3-methallylhydrogensulfidopalladium (6, 6 a) with n-butyl-lithium crystalline compounds having the composition RC3H4PdSLi(THF)≈4, R = H, CH3 (7, 7 a) are obtained; their 1H NMR spectra also reveal the existence of the two stereoisomers having C3h and Cs symmetry. The same type of stereoisomerism is observed with the crystalline [(n-C4H9)4N]+[(η3-C3H5Pd)3S2]- (8) obtained from 7 and (n-C4H9)4N+ClO4
-. For 7 and 7 a an ionic structure consisting of trigonal bipyramidal (η3-RC3H4Pd)3S2- anions and Li3S(THF)4+ cations is proposed.
Gasphasen-Reaktionen, 35. Benzseleniren als kurzlebiges Zwischenprodukt in der Pyrolyse von 1.2.3-Benzoselenodiazol zu 6-Fulvenselon/ Benzselenirene as Short-lived Intermediate in the Pyrolysis of 1,2,3-Benzoselenodiazole to 6-Fulvenselone
Authors: Bock Hans , Aygen Sitki , Solouki Bahman
Published: February 2015

In the pyrolysis of 1,2,3-benzoselenodiazole using a short-distance furnace, a short-lived intermediate is detected photoelectron spectroscopically. Mass spectra recorded under similar conditions suggest an isomer C6H4Se rearranging to the more stable final product 6-fulveneselone. The ionization pattern obtained by computerized spectra stripping is assigned to benzselenirene by molecular radical cation state comparison based on MNDO calculations.
Untersuchungen über Substituenten-Einflüsse auf die reduktive Eliminierung des Biphenyl-Systems aus cis-Bis(aryl)bis(triphenylphosphan)platin(II)-Verbindungen/ Influence of Substituents on the Reductive Elimination of the Biphenyl-System from cis-Bis(aryl)bis(triphenylphosphane)platinum(II) Compounds
Authors: Bayer Ulrich , Brune Hans Albert
Published: February 2015

Compounds cis-[Pt(PPh3)2(3-X-C6H4)2] [X = F, Cl, CF3, CH3O, (CH3)2N] and cis- [Pt(PPh3)2(3-X-C6H4)(Y-C6H4)] [X = F / Y = H, 4-F, 4-CF3, 4-CH3O; X = Cl/Y = 4-F; X = CF3 /Y = 4-F; X = CH3O/Y = 4-F] have been synthesized and studied thermally with respect to the reductive elimination of disubstituted biphenyls. Activation parameters ⊿H≠ and ⊿S≠ are reported and discussed.
Zur intermediären Existenz von Ethylenfluoronium-Ionen in der Gasphase/ On the Intermediary Existence of Gaseous Ethylen Fluoronium Ions
Authors: Ciommer Bernhard , Schwarz Helmut
Published: February 2015

The long-sought ethylen fluoronium ion (2) is generated as an intermediate in the dissociative ionization of 1-fluoro-2-(p-methyl)phenoxy ethane (4). However, prior to collisionally induced dissociation 2 undergoes ring-opening, associated with hydrogen migration, to form 1-fluoroethyl cation (3). Other decomposition pathways of the molecular ions of 4 involve (i) direct formation of 3 via a combination of C-O-cleavage (loss of ArO -) and [1,2] hydrogen migration (18%) and (ii) complete positional loss of the a-and β-methylene hydrogen atoms (34%). The remaining 48% of the molecular ions of 4 dissociate via anchimeric assistance of the fluorine in the elimination of ArO·, thus giving rise to the formation of 2.
Amino Acids as Substrates in the Synthesis of Substituted Organocobalamins
Authors: Maihub Abdussalam , Grate Jay W. , Xu Hui Bi , Schrauzer Gerhard N.
Published: February 2015

The amino acids alanine, valine, leucine, isoleucine, norvaline, α-amino butyric acid, and β -methyl aspartic acid are utilized as substrates for organocobalamin syntheses under “oxidizing/reducing” conditions. In the presence of V+3 as the reducing agent, free radicals are generated by the reaction of oxygen radicals with the amino acids through hydrogen atom abstraction. These amino acid radicals then combine with the cobalt atom of vitamin B12r to yield the respective organocobalamins. The cobalamin obtained from the reaction of β-methyl aspartic acid is a possible intermediate in the coenzyme B12 dependent skeletal rearrangement of β-methyl aspartic acid to glutamic acid. HPLC analysis of the cobal-amins prepared from D, L-alanine indicates that the corrin ligand is relatively ineffective at promoting asymmetric syntheses under these conditions.
[4 + 2] -Photocycloaddition eines Organoeisendienophils mit 1.3-Dienen/ [4 + 2]-Photocycloaddition of an Organoiron Dienophile with 1,3-Dienes
Authors: Battaglia R. , Frazier C. C. , Kisch H.
Published: February 2015

A tricyclic 1,1,1-tricarbonyl-2,3,1-diazaferrole derivative (1) reacts photochemically with 1,3-dienes with formation of [4 + 2]-cycloadducts. Introduction of substituents in the 1- or 1,4-positions of the diene or of electron releasing groups in the dienophile results in an inhibition of the cycloaddition. The reaction proceeds stepwise via photodissociation of carbon monoxide, coordination of the diene to iron, intramolecular photocycloaddition, and re-uptake of carbon monoxide. No cycloaddition occurs if the complexed diene is allowed to react thermally. X-ray structural analyses of 1 and its cycloadduct with 2,3-dimethylbutadiene (3d) reveal the presence of a novel type of three electron metal - diazene bond for both compounds and delocalized bonding for the diazaferrole 1.
Notizen: Synthesis of Trialkylstannanedithi ocarboxy lato Rhenium(I) Complexes [1]
Authors: Hättich Thomas , Kunze Udo
Published: February 2015

Novel trialkylstannanedithiocarboxylato complexes are formed in a one-pot reaction of R3SnCS2Li (R = benzyl, methyl, cyclohexyl) with BrM(CO)5 (M = Mn, Re) in a THF/dioxane solution. Tetracarbonylmetal species could be detected by IR spectroscopy in all cases. The more stable rhenium chelate complexes, R3SnCS2Re(CO)4, were isolated by chromatographic separation as yellow, low-melting solids with 10-20% yield.
Notizen: Photodimerisierung von 6-trans-Styryl-4- methoxy-2-pyr on ( = 5.6-Dehydrokawain) und cis-Isomerisierung von ( ± )-Kawain/ Photodimerisation of 6 -1 rans-Styry 1 - 4 - methoxy- 2 - pyrone ( = 5,6-Dehydrokawain) and cis-Isomerisation of (±)-Kawain
Authors: Kaloga Macki , Christiansen Ilona
Published: February 2015

The photochemical transformation of 5,6-Dehydrokawain (1) to rel-(lR,6S,7S,8S)-5-methoxy-7-phenyl-8-[6-(4-methoxy-2-pyronyl)]-1-(E)-styryl-2-oxabicyclo[4,2,0]octa-4-en-3-one (2) by irradiation with a light bulb [1] is con-firmed. Kawain (3) turns out to be resistent to photochemical reaction in several tests. During irradiation by a Hg-lamp a transformation to cis-Kawain (4) takes place, however.
Über Oxoplumbate(IV) Die Kristallstruktur von HT-Li2PbO3 [1] The Crystal Structure of HT-Li2PbO3 [1] / On Oxoplumbates(IV) The Crystal Structure of HT-Li2PbO3 [1]
Authors: Brazel Berthold , Hoppe Rudolf
Published: February 2015

Single crystals of HT-Li2PbO3 have been prepared by heating of mixtures of Rb2PbO3 and Li2O [Ag-cylinders, 600 °C, 100 d]. The structure determination [1005 symmetry independent l0(hkl), R = 5.85%, Rw = 5.35%, confirms space group C2/c with a = 548.60(16), b = 949.51(22), c = 1027.35(27) pm, β = 100.11(3)°, drö = 6.78 g · cm-3 , dpyk = 6.80 g · cm-3 , Z - 8. The NaCl-type structure variant is characterized by alter-nating layers of Li+ and Pb4+ /Li+ cations, which are all octahedrally coordinated. Effective Coordination Numbers, ECoN are calculated via Mean Fictive Ionic Radii, MEFIR.
Phases of Decaphenylcyclopentagermane (Ph2Ge)5 [1] / Phases of Decaphenylcyclopentagermane (Ph2Ge)5 [1]
Authors: Roß Ludwig , Dräger Martin
Published: February 2015

(Ph2Ge5) can be obtained from solutions in five crystalline phases, two pure and three including solvent of crystallization. This is lost at 70 °C. At 190 °C all phases transform into a plastic crystalline phase. For this tetragonal phase a gear wheel model for librations of the molecules is developed. The crystal structure of triclinic (Ph2Ge)5 has been determined and refined to R = 0.050. The molecule has a flexible conformation in accordance with a better solubility than exhibited by the homologous rings (Ph2Ge)4 and (Ph2Ge)6 containing rigid normal conformations. The arrangement of phenyl groups is either parallel or perpendicular for both cases intra- and intermolecular. The compound (Ph2Ge)6 attains a plastic crystalline state at 346 °C.
Über Hydraziniumsalze von Iodoplatinaten / On Hydrazinium Salts of Iodoplatinates
Authors: Thiele Gerhard , Wittmann Kurt
Published: February 2015

The new compounds (N2H5)2PtI6 and (N2H5)2PtI5 · H2O were obtained by reaction of H2PtCl6 with N2H5CI and HI in aqueous solutions. In the crystal structure of the ortho - rhombic bis[hydrazinium(+I)]hexaiodoplatinate(IV) (N2H5)2PtI6 the N2H5+ cations and PtI6
2- anions build up a K2PtCl6- like arrangement. Bis[hydrazinium(+I)]pentaiodoplatinate( II,IV)hydrate, (N2H5)2Ptl5 · H2O, is classed with the group of linear chain mixed-valence platinum complexes which have highly anisotropic properties. In the crystal structure are structurally undistinguishable PtI4-units (Pt-I = 264 pm) connected by asymmetric I-bridges (Pt-I = 270 pm and 338 pm) to 1 [PtI4I2/2] chains.
Darstellung und spektroskopische Charakterisierung von Hexachloroosmat(V) / Preparation and Spectroscopical Characterisation of Hexachloroosmate(V)
Authors: Preetz W. , Bruns M.
Published: February 2015

(TEA)[OSCl6] is formed quantitatively by heating solid trans-(TEA)[OsX4(CO)2] (X = Br, I) in a stream of chlorine at 120 °C, and can be purified by recrystallisation from CH2Cl2 without decomposition. It is reduced immediately by acetone, methanol, Cl-, Br-, I- to give [OsCl6]2-. The standard potential [OsCl6]-/[OsCl6]2- in acetonitrile referred to the saturated mercury-mercurous sulphate electrode is 0.840 V. The IR and Ra bands of (TEA)[OsCl6], assigned according to point group Oh, are shifted to higher frequencies compared with (TEA)2[OsCl6]. The excitation at 488.0 nm gives a resonance Raman spectrum exhibiting 6 overtones of vi and combination tones up to 4ν1 + v5. The electronic absorption spectrum shows five spin-forbidden intraconfigurational transitions coupled with odd vibrational modes in the near infrared region. The spin-allowed 4A2g → 4T2g,4T1g-transitions are observed at 347 and 305 nm. The excited levels can be fitted with the parameters ⊿ = 28500 cm-1, B = 340 cm-1, ξ = 2500 cm-1 , allowing to calculate the nephelauxetic ratio β55 to 0.47. In the visible region extensive charge transfer transitions are observed. Based on the strong oxidizing character of Os(V) there is a bathochromic shift of corresponding bands of [OsCl6]- in relation to [OsCl6]2- of about 6600 cm-1 and to the isoelectronic [ReCl6]2- of about 13700 cm-1, respectively. From πt1u→dt2g the optical electronegativity is calculated to Xopt(Osv) = 2.49.
Beiträge zur Chemie des Bors, 133 [1] Molekül-und Kristallstruktur von Tris(methylanilido)boran / Contributions to the Chemistry of Boron, 133 [1] Molecular and Crystal Structure of Tris(methylanilido) Borane
Authors: Nöth Heinrich
Published: February 2015

The title compound crystallizes in the rhombohedral space group R3, Z = 1. The boron atom occupies a special position on the threefold axis therefore imposing C3 symmetry to the molecule. The C2BN plane is twisted relative to the BN3 plane by 37.1°, and the BN bond length of 144.8(3) pm is on the upper limit of BN bond lengths found for other triaminoborane systems.
Chromatographische Trennung schwefelhaltiger Heterocyclen der Typen (CH2)nSm und SenS8-m mittels HPLC [1] / Chromatographie Separation of Sulfur Containing Heterocycles of Type (CH2)nSm und SenS8-m by HPLC [1]
Authors: Steudel Ralf , Strauss Eva-Maria
Published: February 2015

The Separation of a number of cyclic methylene sulfides and selenides by reversed-phase high-pressure liquid chromatography is reported. The retention times as well as the capacity factors depend in a systematic way on the ring size, the number and kind of chalcogen atoms, and the number of heteronuclear bonds within the ring. These relation-ships are used to assign the chromatograms of cyclic selenium sulfides of type SenS8-n (n = 1-8) prepared in a new reaction from Se2Cl2, SCl2 and potassium iodide and containing all selenium atoms in neighboring positions.
Synthese und Struktur von C5Me5Pd(PR3)X: Palladiumkomplexe mit einem unsymmetrisch gebundenen Pentamethylcyclopentadienylring [1] / Synthesis and Structure of C5Me5Pd(PR3)X: Palladium Complexes with an Unsymmetrically Bonded Pentamethylcyclopentadienyl Ring [1]
Authors: Kraus H.-J. , Werner H. , Krüger C.
Published: February 2015

The complexes C5Me5Pd(PR3)X (1-4) are prepared from [Cl(PR3)Pd]2(μ-OCOCH3)2 and TIC5Me5. Attempts to replace the halide ligand by a second C5Me5 or a C5H5 unit remained unsuccessful. The X-ray structure analysis of C5Me5Pd[P(i-Pr)3]Cl (3) indicates that the five-membered ring shows a tendency of η1-bonding towards the metal.
Sila-Pharmaka, 31. Mitt. [1] Synthese, Struktur und pharmakologische Eigenschaften von Diphenyl(2-piperidinoethoxymethyl)silanol und seinem Kohlenstoff-Analogon / Sila-Pharmaca, 31 th Communication [1] Synthesis, Structure, and Pharmacological Properties of Diphenyl(2-piperidinoethoxymethyl)silanol and its Carbon Analogue
Authors: Tacke Reinhold , Lange Hartwig , Sheldrick William S. , Lambrecht Günter , Moser Ulrich , Mutschier Ernst
Published: February 2015

In the course of systematic investigations on sila-substituted parasympatholytics the diphenyl(2-aminoethoxymethyl)silanols 3b and 4b (and its carbon analogue 4a) were synthesized and characterized by their physical and chemical properties. In the solid state 4a and 4b form strong O-H---N hydrogen bonds, which are intramolecular (4a) and intermolecular (4b), respectively. 4a and 4b were found to be weak antimuscarinic agents (4b >4a) and strong papaverine-like spasmolytics (4a ≈4b).
Koordinationschemie funktioneller Phosphorylide, V [1] Die Molekülstrukturen der isomorphen Mangan-und Rheniumbromtricarbonyl- komplexe von 2-Methyl-2-(triphenylphosphonio)dithiopropionat / Coordination Chemistry of Functional Phosphorus Ylides, V [1] The Molecular Structures of the Isomorphous Manganese and Rhenium Bromotricarbonyl Complexes of 2-Methyl-2-(triphenylphosphonio)dithiopropionate
Authors: Winter Werner , Merkel Reinhard , Kunze Udo
Published: February 2015

The isomorphous crystal structures of the manganese and rhenium bromotricarbonyl complexes 2 a, b have been determined at room temperature (Mn) and at -110 °C (Mn, Re; P21/c, Z - 4). At room temperature, data collection is accompanied by crystal decomposi-tion, and a cleavage of the PPh3 group is suggested by the results as the primary process. The same initial step is thought to be valid for the photodecomposition in solution. The main structural difference between the free and coordinated betaine ligand 1 is the reduced electrostatic interaction of P and S in the complexed form.
Preparation and Stereochemistry of 12a-Hydroxymethyl Derivatives of Rotenone and Amorphigenin
Authors: Kostova I. , Ognyanov I.
Published: February 2015

A convenient method for the preparation of 12a-hydroxymethyl derivatives of rotenone 1 and amorphigenin 2, possibly applicable to other rotenoids with activated 12a-hydrogen atom is described. The stereochemistry of the products is discussed.
"Ag8SnTe6" — Ein neuer stabiler Vertreter der Argyrodite ? "Ag8SnTe6" -a New Stable Argyrodite ?
Authors: Gather Bernd , Blachnik Roger
Published: February 2015

DTA, X-ray and microprobe measurements show, that the compound "Ag8SnTe6" seems not to be a stable argyrodite.
Luminescence of CS3V2O4F5
Authors: Blasse G. , Dirksen G. J.
Published: February 2015

The compound CS3V2O4F5 with statistically distributed [V2O4F5]3- complexes shows a weak, red emission at low temperatures. This emission is discussed in relation to similar luminescent compounds.
Bindungsverhältnisse und magnetische Eigenschaften ternärer Arsenide ET2As2 / Bonding and Magnetic Properties in Ternary Arsenides ET2As2
Authors: Pfisterer Martin , Nagorsen Günter
Published: February 2015

The interatomic distances of ternary arsenides ET2As2 with ThCr2Si2-structure were determined by X-ray powder methods (E = Ca, Sr, Ba; T = Cr, Fe, Co, Ni, Cu). The phases were found to behave according to the Zintl-Klemm-Busmann concept. Magnetic susceptibilities were measured.