bluuebunny/crossref_metadata_2025 huggingface dataset:
Na2AuAs, Na2AuSb, K2AuSb - drei neue A2BX-Verbindungen mit B-X-Kettenstruktur / Na2AuAs, Na2AuSb, K2AuSb - Three New A2BX Compounds with a B-X Chain Structure
Authors: Mues Cornelia , Schuster Hans-Uwe
Published: February 2015

The three new compounds crystallize orthorhombically, space group Cmcm with Na2AuAs: a = 887.1(2) pm, b = 712.9(2) pm, c = 576.0(2) pm;

Na2AuSb: a = 927.9(3) pm, b = 756.2(2) pm, c = 584.1(5) pm;

K2AuSb: a = 1045.9(5) pm, b = 786.1(3) pm, c = 650.0(5) pm.

The structure of Na2AuAs and Na2AuSb contains Au-As(Sb) zigzag chains in which the Au atoms are linearly bonded to the 5b-elements. The powderdiagram shows the phase K2AuSb to be isotypic to Na2AuAs and Na2AuSb.
Tetrazido-Nitrido-Molybdat(VI); Darstellung, IR-Spektrum und Kristallstruktur von AsPh4[MoN(N3)4] / Tetrazido-nitrido-molybdate(VI); Preparation, IR Spectrum and Crystal Structure of AsPh4[MoN(N3)4]
Authors: Dehnicke Kurt , Schmitte Josef , Fenske Dieter
Published: February 2015

The complex AsPh4[MoN(N3)4] is prepared by the reaction of AsPh4[MoNCl4] with silver azide in dichloromethane suspension in the presence of dry sodium sulfate. The IR spectrum indicates an Mo≡N group and four covalently bonded N3 groups for the [MoN(N3)4]⊖ anion. AsPh4[MoN(N3)4] crystallizes in the triclinic space group P1̄ with two formula units in the unit cell. The crystal structure was solved by X-ray diffraction methods (R = 0,038; 4049 independent reflexions). The structure consists of AsPh4⊕ cations and [MoN(N3)4]⊖ anions. The short MoN bond length of the nitrido ligand (163 pm) corresponds to an Mo ≡ N triple bond. The steric effects of the lone pairs of the α-N atoms of the azido groups with tho MoN ligand cause a propellerlike twisted conformation of the four azido groups.
Zur Struktur und Komplexchemie von Phosphinoderivaten des 5-Methoxy-2(5H)-furanons / Structure and Coordination Chemistry of Phosphino Derivatives of 5-Methoxy-2(5H)-furanon
Authors: Fenske D. , Prokscha H. , Stock P. , Becher H. J.
Published: February 2015

With R2PSi(CH3)3 (R = C6H5, i-C3H7, t-C4H9) one Cl atom of 3,4-dichlor-5-methoxy-2(5 H)-furanon (1) is substituted by the R2P group. An x-ray crystal structure analysis of the phosphino derivative with R = C6H5 (2) it has shown that of the two Cl atoms in 1 only the β-position (to C= O) is substituted. The coordination chemistry of 2 and its bis- (diphenylphosphino) derivative (3) is studied by preparation of the compounds 2 · Mo(CO)5 and 3 · Mo(CO)4. With PdCl2 · 2 C6H5CN (2) gives a dinuclear complex [2 · PdCl2]2, with bridging Cl atoms. The structure is established by a comparison with the similar complex of PdCl2 and 2-chloro-diphenylphosphino-maleic acid dimethylestor, which was synthe­sized as a model compound and studied by x-ray crystal structure analysis.
Übergangsmetall-Carbin-Komplexe, LX [1]. Neue Triphenylsilyl-Carben-Komplexe des Rheniums durch Umsetzung eines kationischen Carbinkomplexes mit Nucleophilen / Transition Metal Carbyne Complexes, LX [1] Novel Triphenylsilyl Carbene Complexes of Rhenium by Reaction of a Cationic Carbyne Complex with Nucleophiles
Authors: Fischer Ernst Otto , Rustemeyer Paul , Neugebauer Dietmar
Published: February 2015

The reaction between C5H5Re(CO)3 and LiSi(C6H5)3 affords the compound C5H5(CO)2ReC(OCH3)Si(C6H5)3 after subsequent alkylation with CH3SO3F. This complex reacts with BF3 to yield [C5H5(CO)2ReCSi(C6H5)3]BF4. This cationic carbyne complex yields C5H5(CO)2ReC(CH1)Si(C6H5)3 with LiCH3 and C5H5(CO)2ReC(H)Si(C6H5)3 with (C4H9)4NBH4. Reaction conditions, properties and spectroscopic data of the new com­pounds as well as an X-ray structure determination of C5H5(CO)2ReC(H)Si(C6H5)3 are reported.
Synthese von vier- und achtgliedrigen Heterocyclen, die Schwefel, Stickstoff und Phosphor enthalten, und die Röntgenstrukturanalyse eines phosphorhaltigen achtgliedrigen SN-Ringes / Synthesis of Four- and Eight-Membered Heterocycles Containing Sulfur, Nitrogen and Phosphorus and the X-ray Structure of a Phosphorus-Containing Eight-Membered SN-Ring
Authors: Roesky Herbert W. , Mehrotra Sushil K. , Platte Christoph , Amirzadeh-Asl Djamrnschid , Roth Bernhard
Published: February 2015

Eight-membered rings of the composition [SO2(NR)2PR′]2 3a-d with R = CH3, C2H5, and R′ = CH3, C6H5, were prepared from substituted sulfamides and dichlorophosphanes in the presence of a tertiary amine. These molecules were characterized on the basis of 1H and 31P NMR investigations and of mass spectra. 3 a reacts with phosphorus pentachloride to yield the spirocyclic derivative 4 with the phosphorus atom in the center of two four-membered rings. Methyliodide reacts with 3 a and 3 b under opening of the eight- membered ring and formation of phosphonium salts. The structure of 3 b is discussed in detail. 8b crystallizes in the orthorhombic space group Pna 21 with a = 12.60(0), b = 13.27(1), c = 12.62(4) Å.
Das Kraftfeld von SF4 / The Force Field of SF4
Authors: Sawodny Wolfgang , Birk Karl , Christe Karl O.
Published: February 2015

As it proved impossible, to compute a unique and meaningful General Valence Force Field for SF4 from the known experimental data, this was realized by an ab initio cal­culation using a basis set of 3-3-21 + 1 d G functions for the S-, and 4-21 G functions for the F-atom. The values of the stretching force constants are f (S-Feq): 5.36 mdyn/Å, f(S-Fax): 3.25 mdyn/Å. Problems of assignment of the deformational modes could be settled conclusively.
The Structure of Thiodithiazyl Derivatives. An Example of an Electron-Rich-Four-Center-Bond
Authors: Gleiter Rolf , Bartetzko Richard , Hofmann Peter
Published: February 2015

Experimental and computational evidence indicates that the five-membered ring system S3N2
+ has an 2A2 ground state. Different possibilities for the stabilization of S3N2
+ are discussed on the basis of MO arguments and calculations using semiempirical and ab initio (STO 3G) methods. The theory allows the rationalization of the structures of S3N2Cl2, S3N2X and [S6N4]2+. The bonding between the two S3N2
+ moieties in [S6N4]2+ is described as an electron rich six electron four center bond.
Kristallstruktur von Hexakis (thiazylfluorid) nickel (II)-hexafluoroarsenat / Crystal Structure of Hexakis(thiazylfluoride)nickel(II) Hexafluoroarsenate
Authors: Hartmann Gabriele , Jones Peter G. , Mews Rüdiger , Sheldrick George M.
Published: February 2015

The structure of the title compound has been determined from X-ray diffractometer data. It is isostructural with the cobalt derivative [1].
Vier-und fünfgliedrige Phosphorheterocyclen, L [1] Tautomeric und Substitution am 5 -Dimethylamino -1.2.4.3λ3-triazaphosphol [2] / Four- and Fivemembered Phosphorus Heterocycles, L [1] Tautomerism and Substitution at 5-Dimethylamino-l,2,4,3λ3 -triazaphosphole [2]
Authors: Schmidpeter Alfred , Tautz Helmut
Published: February 2015

1,2,4,3 λ3 -Triazaphospholes unsubstituted at the heteroatoms can be synthesized only if they carry an amino group in 5-position. The title compound, being the first representative, was prepared from N,N-dimethyl-N′-aminoguanidinium iodide and P(NMe2)3. Its single proton is not bonded to phosphorus but to nitrogen and causes association by NH···N bridges. The proton was substituted for silyl, stannyl, phosphino and thiophosphinyl groups assumedly in 2-position. The phosphino derivatives react with sulfur only at the exocyclic phosphorus. Loss of N2 from the triazaphosphole ring was observed in one case.
Crystal and Molecular Structure of the Linear Chain Bis(1,2-diaminopropane)platinum(II,IV)tribromide
Authors: Endres H. , Keller H. J. , Martin R. , Nötzel S.
Published: February 2015

[Pt(dapn)2]Br3 (dapn = 1,2-diaminopropane), ortho-rhombic, Immm (D25
2h), a = 5.338(1), b = 6.900(5), c= 19.738(4) Å, Z = 2, V= 727 Å3 , dc = 2.7 g · cm-3 . The structure was refined to R = 0.094 for 576 reflections and can be described as a Wolffram's salt analogue. A rotating crystal photograph shows weak diffuse layers between the Bragg reflections as evidence for one-dimensional order along the M-X-M chain, but for successful refinement the M-X distance (2.673(1) Å) have to be assumed to be equal.
cis-trans-Configuration of α-Azidochalkones
Authors: Knittel Dierk , Weber Gabriela
Published: February 2015

The two stereoisomeric α-azidochalkones (1,3-diaryl-2-azidopropenones) are selectively obtain-able, depending on the temperature, by condensation of aldehydes with a-azidocarbonyl compounds. For the higher melting point compound the trans configuration is proved by single crystal X-ray analysis of its triphenyl-phosphazeno derivative.

Analogous isomers may now be characterised from their 1H NMR parameters.
Short Time Pyrolysis, Part 11 [1-3]A Simple Synthesis of Dibenzopyracylene
Authors: Schaden Gerhard
Published: February 2015

Dibenzo[b,def]chrysene-7,14-dione (1) and benzo[rst]pentaphene-5,8-dione (2) on vacuum flow pyrolysis successively eliminate two CO's forming 13H-naphtho[3,2,1-cd]fluoranthene-13-one (3) and finally indeno[1,2,3-cd]fluoranthene (dibenzopyracylene) (4).
Neue phosphororganische Liganden: 2-Pyridyl-phosphane, -phosphanmethylene und -phosphanborane / New Organophosphorus Ligands: 2-Pyridyl-phosphanes, -phosphanemethylenes, and -phosphaneboranes
Authors: Schmidbaur Hubert , Inoguchi Yoshio
Published: February 2015

Diphenyl(2-pyridyl)phosphane, bis-2-pyridyl(phenyl)phosphane, and tris-2-pyridylphosphane (1a-c) are prepared from 2-pyridyl-lithium and the corresponding chlorophosphanes. These phosphanes can be converted into the methylene compounds via the methylphosphonium salts 2a-c. The ylids 3a-c and their precursors were characterized by a detailed 1H, 13C, and 31P NMR study. 3 c is thermally unstable and undergoes a spontaneous condensation reaction. The three related phosphaneboranes 4a-c can be obtained in the reactions of 1 a - c with tetrahydrofuran-borane. The BH3 groups are selectively bonded to the phosphorus atoms. - 1 c forms insoluble 1 : 1 complexes with CuCl and AgCl, but a soluble adduct with AuCl (5 c, 6 c, and 7 c, respectively). A similar AuCl complex is formed from (CO)AuCl and 1 a . In both gold compounds the ligands are solely P-bonded.
Struktur und Eigenschaften des Kaliumhydrogendiarsenit-Hemihydrats, KHAs2O4 · 1/2 H2O / Structure and Properties of the Potassiumhydrogendiarsenite-hemihydrate, KHAs2O4 · 1/2 H2O
Authors: Fuchs Joachim , Guevara Hernan
Published: February 2015

KHAs2O4 · 1/2 H2O crystallizes in the tetragonal space group I 4/m with the lattice constants a = 14,480 Å, c = 5,250 Å. The anion forms infinite chains, [HAs2O4]n
n- , in the direction of the c axis. Arsenic is surrounded by three oxygens in trigonal pyramidal co-ordinations.

Ultracentrifuge work shows that the solution contains monomeric species, probably [ASO(OH)2]-. Raman spectra gave no evidence for the existence of As-H-bonds either in the solid or in solution.
Spektroskopische Untersuchungen in der Festkörperchemie, XIII. Temperaturabhängigkeit der 127I-Kernquadrupolkopplung in NH4IO4 und anderen Periodaten / Spectroscopic Investigations in the Solid State Chemistry, XIII. Temperature Dependence of the 127I-Nuclear Quadrupole Coupling in NH4IO4 and other Periodates
Authors: Burkert Paul K.
Published: February 2015

The temperature dependence of the electric field gradients was measured by I. and II. order quadrupole effects of the 127I NMR signals in scheelite-structured NH4IO4 and RbIO4, in pseudo-scheelite CsIO4 and in N(CH3)4IO4, where rcation > ranion- An interpretation of the anomalous positive temperature dependences of the quadrupole coupling constants in NH4IO4 and in the isostructural NH4ReO4 is proposed.
Ringkontraktion am Cyclotrisilazan -System - Synthese und Molekülstrukturen zweifach silylverknüpfter Cyclodisilazane / Ring Contraction in the Cyclotrisilazane System - Synthesis and Molecular Structures of Silyl-Bridged Cyclodisilazanes
Authors: Clegg William , Hesse Michael , Klingebiel Uwe , Sheldrick George M. , Skoda Lutz
Published: February 2015

l-(Fluorodiorganylsilyl)-2,2,4,4,6,6-hexamethyl-3-(trimethylsilyl)cyclotrisilazanes react with butyllithium to give the corresponding lithium salts. Ring contraction of the lithium salts with formation of lithiated (fluorodiorganylsilyl)amino-substituted four-membered rings is observed in THF solution. The dimerisation of these cyclodisilazanes with elimination of LiF is demonstrated by crystal structure determinations of three products. Monoclinic and triclinic crystalline modifications of one compound could be isolated.
Darstellung, Eigenschaften und Kristallstruktur von 6-Methyl-4-Methylen-2-Phenyl-4 H-1.3.2-dioxaphosphorin / Preparation, Properties and Crystal Data of 6-Methyl-4-methylen-2-phenyl-4 H-1,3,2-dioxaphosphorin
Authors: Seyerl J. v. , Huttner G.
Published: February 2015

PPh(C6H5O2) was prepared for the first time in the free state. The compound crystallizes in the monoclinic spacegroup P21/c; a= 1084, b= 1079, c= 989 pm; β= 113.7°.
X-ray Structural Analyses of Two Allotropes of Cycloheptasulfur ( γ and δ-S7 ) [1]
Authors: Steudel Ralf , Steidel Jürgen , Pickardt Joachim , Schuster Fritz , Reinhardt Richard
Published: February 2015

X-ray structural analyses of two monoclinic allotropes of cycloheptasulfur carried out at -110 °C revealed almost identical chair-like molecular structures of approximate Cs symmetry with bond distances between 199.5 and 218.2 pm, bond angles between 101.5 and 107.5°, and torsional angles between 0 and 109°.
O.O-Diphenyl-N-chloramidophosphat / 0,0-Diphenyl-N-chlorophosphoramidate
Authors: Drewelies Kurt , Münch Volker , Jander Jochen , Latscha Hans Peter
Published: February 2015

(C6H5O)2P(O)NHCl can be synthesized in 83-88% yield by direct hydrolysis of (C6H5O)2P(O)NCl2 in petroleumether solution. This first example of a new class of N-halogeno compounds, a colourless crystalline substance was characterized by 31P and 1H NMR, IR and mass spectroscopy as well as by elemental analysis.
Arsenverbrückte zweikernige Mn(CO)4Br-Komplexe / Arsenic Bridged Dinuclear Mn(CO)4Br Complexes
Authors: Börner Michael , Müller Rainer , Vahrenkamp Heimich
Published: February 2015

In Mn(CO)5Br one or two CO groups could be replaced by Me2AsCl. From Me2AsCl-Mn(CO)4Br with carbonyl metalates, or from Mn(CO)5Br with organometal dimethylarsenides, the arsenic bridged dinuclear complexes LnM-AsMe2-Mn(CO)4Br with LnM = CrCp(CO)3, MoCp(CO)3, WCp(CO)3, and Mn(CO)5 were obtained. Upon attempts to convert these to metal-metal bonded compounds the Cr-As-Mn complex decomposed whereas the Mn-As-Mn complex was spontaneously converted to (CO)4Mn[μ-AsMe2, μ-Br]Mn(CO)4.
Synthese und Reaktionen von Enaminosulfoniumsalzen / Syntheses and Reactions of Enaminosulfonium Salts
Authors: Braun Heinz , Amann Anton , Barnert Robert , Firl Joachim
Published: February 2015

A general method for preparing (E)-alkylamino and dialkylamino vinylsulfonium salts is reported. The hydrolysis and some alkylation and acylation reactions have been examined. The 2,2-dihydroxyethyl sulfonium salt (9 a) is produced by acid hydrolysis of 4 a. In the reaction of 4h with trimethyloxonium salt and acyl halides the N-alkylated and N-acylated products 4 a and 11 are formed respectively. (E)-N,N-diacylated compounds (12) are obtained from 41 and 51 by the reaction with excess acyl halides. On treatment with base, 11a forms mixtures of the (E)- and (Z)-sulfonium imido ylides 14 and 15.
Synthese von cis-und trans-4-Cyanocyclohexanol / Synthesis of cis-and trans-4-Cyanocyclohexanol
Authors: Praefcke Klaus , Schmidt Dietmar
Published: February 2015

The synthesis of cis-and trans-4-cyanocyclohexanol 2 a and 2 b is described for the first time. Their stereochemistry has been determined by 1H NMR spectroscopy.
A Comparison of the Effects of Steric Crowding at Phosphorus on the Steric Course of Wittig Reactions of Stabilised and Semistabilised Ylides
Authors: Allen David W.
Published: February 2015

The cis-trans ratio of the alkenes formed in Wittig reactions of semistabilised ylides (derived from benzyltriarylphosphonium salts in ethanolic sodium ethoxide) with benz-aldehyde, acetaldehyde or trimethylacetaldehyde increases as steric crowding at phos-phorus increases. In contrast, the cis-trans ratio of the unsaturated esters formed in the related reactions of the stabilised ethoxycarbonylmethylene ylides decreases as steric crowding at phosphorus increases. The relevance of these results to recent proposals for the mechanism of the Wittig reaction is considered.
NOTIZEN. The Conformations of Oxacyclooctanes
Authors: Burkert Ulrich
Published: February 2015

The geometries and energies of the conformers of oxocane, the isomeric di-and trioxocanes, and of 1,3,5,7-tetroxocane were calculated by molecular mechanics. A boat-chair conformation was preferred by all molecules. From the preference of oxygen in the boat-chair conformations of oxocane (position 3 over 1 over 4) the preferred boat-chair form of all other oxocanes can be derived. The results are compared to experi-mental data, which in part can be reinterpreted. Additional CNDO/2 and MINDO/3 calculations were performed for 1,3,5,7-tetroxocane.
Polarographic Behaviour of Some Steroidal Olefins
Authors: Wilk Manfred , Schmitt Karlheinz
Published: February 2015

Halve-wave-potentials of five steroidal olefins were measured by anodic polarography. They show oxidation-potentials in the range of 0.7-0.9 V. Differences in potentials are correlated to shape of the molecules.
Eine neue Synthese und das IR-Spektrum von Osmiumpentachlorid / A New Synthesis and the IR Spectrum of Osmiumpentachloride
Authors: Dehnicke Kurt , Lößberg Rainer
Published: February 2015

Osmiumpentachloride is prepared by the reaction of osmiumtetroxide with sulfur - dichloride. X-ray powder data gave identical results with those of other authors; however, the IR spectrum differs from the reported data. With AsPh4
+Cl- in trifluortrichlorethane suspension the complex AsPh4[OsCl6] is formed, which can easily be reduced by dichloromethane to osmium(IV), forming the well known hexachloroosmate(IV), (AsPh4)2[OsCl6].
Synthesis and Physico-Chemical Properties of Alcoholato Cobalt(II) Chlorides
Authors: Singh J. V. , Jain N. C. , Mehrotra R. C.
Published: February 2015

Alcoholato complexes of cobalt(II) chloride with the general formula, COCl2 · xROH (where R = Me, Et, Pri, Bui, Bun, Bus and But) have been synthesised by the reactions of anhydrous CoCl2 with an excess of the appropriate alcohols under reflux. Physicochemical studies such as electronic, infra-red spectra, magnetic and conductivity measurements have been carried out to throw light on the structure of these complexes. Magnetic and electronic spectra suggest an octahedral environment for cobalt(II) in the methanolato complex and tetrahedral geometry for all other complexes.
Derivatives of cis-NPCl2(NSOCl)2 and (NPCl2)2NSOCl, Part XV [1]. Methyl-and Ethylamino Derivatives of (NPCl2)2NSOPh
Authors: Cnossen-Voswijk C. , Grampel J. C. van de , Kruk C.
Published: February 2015

The aminolysis of (NPCl2)2NSOPh by methyl-and ethylamine in diethylether proceeds mainly via a non-geminal substitution pattern. In acetonitrile both geminal and non-geminal substitution is observed. The preparation of the derivatives is described and the 1H and 31P NMR data are discussed. The interpretation of the NMR spectra is supported by the simulation of the spectra of NPClNHMeNPCl2NSOPh.
The Crystal Structures of BaSe2 and BaSe3
Authors: Hulliger F. , Siegrist T.
Published: February 2015

BaSe2 crystallizes with a monoclinic cell, a = 9.820(5), 6 = 4.929(3), c = 9.335(5) Å, β= 118.48(5)°; Z = 4, space group C 2/c. BaSe3 is tetragonal, a = 7.2802(5), c = 4.2495(4) Å; Z = 2, space group P4̄21m. Both polyselenides are isotypic with the corresponding poly sulfides.
IR, 31P-, 55 Mn-und 185,187 Re-NMR spektroskopische Untersuchungen an einigen Carbonylmangan-und -rhenium-Komplexen/IR, 31P, 55Mn and 185,187Re NMR Spectroscopic Investigations of Some Carbonylmanganese and -rhenium Complexes
Authors: Keçeci Ahmet , Rehder Dieter
Published: February 2015

The IR and NMR spectra of the complexes [M(CO)6]Cl · HCl (M = Mn: 1, M = Re: 2), M(C0)5C02Et (M = Mn: 3, M = Re: 4), [Mn(CO)5PR3][PF6] (5; PR3 = PPh(OPh)2: a, P(n-Pr)3: b, PHPh2: c, PPh(NEt2)2: d, P(p-C6H4F)3: e), [Re(CO)5PHPh2][PF6] (6 c), Mn2(CO)8(PR3)2 (7) and Re2(CO)8(PHPh2)2 (8c) are discussed in the context of σ-and π-interactions in the metal-ligand system and compared with 51V NMR data of the analogous isoelectronic and isostructural carbonylvanadates (-I). On the basis of these results, the phosphines are arranged in the order of decreasing integral ligand strength according to a>b>c>d. The 55Mn shielding of 5 is greater than that of 1, which is explained by strong σ-interactions and correspondingly large e-a1* splitting dominating the paramagnetic deshielding term in the pseudooctahedral complexes of type 5. The only rhenium compound accessible to NMR is 2, for which the 185 Re and 187 Re resonances were obtained. 31P coordination shifts are positive for all complexes. Spectroscopic data for 7c show that this complex presumably has the structure (CO)5Mn-Mn(CO)3(PHPh2)2, contrasting 7a, 7b, 7d and 7e (local D4d symmetry).
Penta-Coordinated Complexes of Bis(2,4-pentanedionato) Copper(II) with Some Oxygen Donor Organic Solvents
Authors: Baranwal B. P. , Parashar G. K. , Mehrotra R. C.
Published: February 2015

Bis(2,4-pentanedionato) Copper(II) reacts with some oxygen donor organic solvents to form addition complexes with general formula, Cu(2,4-pentanedionato)2. L (where L = MeOH, EtOH, PriOH, ButOH, THF, MeCOMe, MeCOEt and MeCOPrn). The complexes were recrystallized and characterized by the elemental analyses, infrared and electronic spectra, molecular weight and magnetic measurements.
Zur Reaktion zwischen Bortrifluorid und Natrium-diethylphosphit Darstellung und Reaktionen von Tris(diethylphosphitoboran) The Reaction between Borontrifluoride and Sodium Diethylphosphite Synthesis and Reactions of Tris(diethylphosphitoborane)
Authors: Binder Herbert , Palmtag Jürgen
Published: February 2015

Tris(diethylphosphitoborane) (2) can be synthesized by the reaction of BF3·O(C2H5)2 with sodium diethylphosphite. The chemical behaviour of this new compound and its NMR data are reported.
Darstellung und spektroskopische Charakterisierung von Tetrakis (chloro -iodo ) oxalato -osmaten (IV )/Preparation and Spectroscopical Characterisation of Tetrakis(chloro-iodo)oxalato-osmates(IV)
Authors: Preetz W. , Schulz H.
Published: February 2015

On treatment of [OsI4ox]2- with Cl- the mixed complexes [OsClnI4-nox]2-, n = 1, 2, 3, are formed. The isolation and complete separation of the differently coloured geometric isomers is achieved by ion exchange chromatography on diethylaminoethyl cellulose. The IR and Ra spectra are assigned according to point groups C2v, Cs, C1. The mutual influence of ligands, especially by the high trans effect of I, is indicated by shifts of the distinct vibrational and electronic bands. The observed splittings of I→Os transitions are attributed to the different groupings I-Os-I, I-Os-Cl, and I-Os-O, important for the distinction of stereoisomers. The CT-bands as well as the d-d-transitions show batho-chromic shifts with increasing number of I-ligands. Up to five spin-orbit components in the NIR region are well resolved. The assignment is improved by the electronic Ra spectra. The fine structure of some d-d-bands originates from coupling with symmetric vibrational modes.
Kristall-und Molekülstruktur des (Tetramethylcyclobutadien)cis-1.2-dicyano-ethen-1.2-dithiolato-nickel(II) /Crystal and Molecular Structure of (Tetramethylcyclobutadiene)cis-1,2-dicyano-ethene-1,2-dithiolato-nickel(II)
Authors: Hemmer Reinhard , Brune Hans Albert , Thewalt Ulf
Published: February 2015

Single crystals of the title compound, A, have been prepared and studied structurally by X-ray analysis. A crystallizes in the space group P21/n with Z = 4 and lattice parameters a = 11.174(3), b= 15.627(5), c= 8.148(3) Å and β = 92.82(3)°. Within the limits of error the π-bonded cyclobutadiene ring is a square with an average C-C-bond distance of 1.465 Å ; the methyl groups are displaced away from the nickel atom, the average distance between the ring plane and the methyl C-atoms being 0.15 Å. The sulfur containing five membered ring has a cyclic delocalized electron distribution.
Metall-π-Komplexe yon Benzolderivaten, XIII Bis(methylthio-η-beiizol)chrom(0) Darstellung und Einsatz als zweizähniger Chelatligand/ Metal-π Complexes of Benzene Derivatives, XIII Bis(methylthio-η-benzene)chromium(0) Preparation and Function as a Bidentate Chelating Ligand
Authors: Burdorf Helmut , Eischenbroich Christoph
Published: February 2015

The thioanisole-π-complexes (methylthio-η-benzene)-(η-benzene)-chromium (2) and bis(methylthio-η-benzene)chromium (3) have been prepared via lithiation of bis(η-benzene)-chromium and consecutive reaction with dimethyldisulfide. 1H NMR and 13C NMR spectra of 2 and 3 as well as ESR-spectra of the corresponding radical cations 2.+ and 3.+ were recorded and analyzed. In contrast to C(η-arene)-Si and C(η-arene)-P bonds, C(y-arene)-S bonds are stable to solvolysis.

With (norbornadiene)tetracarbonylmolybdenum, 3 readily forms [bis(methylthio-η-benzene)chromium]tetracarbonylmolybdenum (6) wherein 3 functions as a chelating ligand. 1H and 13C NMR evidence suggests, that at room temperature 6 undergoes rapid conformational interconversions.
The Crystal and Molecular Structure of 2-{8-(2-Aminophenoxy)-3,6-dioxaoctyloxy}benzoic Acid · NaClO4, a Linear Polyether with Terminal Amino and Carboxyl Functions
Authors: Chacko K. K. , Saenger W.
Published: February 2015

The title compound, C19H23NO6 · NaClO4, crystallizes in the monoclinic space group P21/c with cell dimensions a = 16.374(5), b = 9.856(4), c = 27.245(8) Å, β = 91.88(5)° and Z = 8. The structure of this polyether complex was solved on the basis of 4501 diffractometer measured reflections and refined to an Rw of 0.091. There are two molecules per asymmetric unit which are related to each other by an approximate non-crystallographic centre of symmetry. Both complex molecules exist in the favourable zwitterion configuration with ion pair attraction between the amino (NH3
+) and carboxyl(COO -) end groups of the polyether ligand. The Na+ion is circulary coordinated to all except the oxygen atoms of the aminophenoxy end group of the polyether ligand suggesting that this oxygen has reduced electronegativity. All C-C and C-O bonds of the ligand exist in favourable gauche and trans conformations.
Synthesis of 6-N-Aryl and Heteroaryl Benzthiazoles as Potential Anthelmintics
Authors: Abuzar Syed , Sharma Satyavan
Published: February 2015

A number of 6-substituted arylaminobenzthiazoles (5-8 and 16-18), 6-(substituted -1-benzimidazolyl)benzthiazoles (9-15) and 6-(3-quinazolyl)benzthiazoles (19) have been synthesized starting from corresponding 6-aminobenzthiazoles. None of the compounds showed significant anthelmintic activity.
Darstellung und Charakterisierung von Tetrabutylammonium-Tetraiodooxotechnetat(V), (TBA) [TcOI4] / Preparation and Characterization of Tetrabutylammonium Tetraiodooxotechnetate(V), (TBA)[TcOI4]
Authors: Peters G. , Preetz W.
Published: February 2015

Pure (TBA)[TcOI4] is prepared from (TBA)[TcOCl4] by ligand exchange reaction with Nal in acetone. The vibrational spectra indicate C4v symmetry for the complex ion. On excitation with the 514.5 nm line of an Ar-laser a resonance Raman spectrum is obtained showing v(TcO) = 996 cm-1 and four of its overtones, symmetrically surrounded by groups of bands arising as well from the sums as from the differences of frequencies with the other fundamentals. In contrast to the ligand exchange reaction the reduction of Tc04- with conc. HI yields products always contaminated with polyiodides. The extremely strong Raman scatterer (TBA)l3 is detected by a characteristic doublet at 111 and 116 cm-1 and even small amounts of it cover the Raman spectrum of (TBA)[TcOI4].
Reaktion von Hiallium(III)-carboxylaten mit Ketonen / Reactions of Thallium(III) Carboxylates with Ketones
Authors: Vollmerhaus Mechthild , Huber Friedo
Published: February 2015

In the reaction of ketones RCOCH3 (R = CH3, C2H5, n-C3H7, i-C3H7, n-C4H9, i-C4H9, tert-C4H9) with thallium(III) acetate in methanol, thallation at CH3 or at a-C in R has been observed by NMR spectroscopy. J(203/205T1-1H) in RCOCH2X [X = Tl(OCOCH3)2] is nearly independent of R (ca. 1290 Hz), but in R′CHXCOCH3 (R′ = H, CH3, C2H5) it increases with increasing chain length. RCOCH2X and R′CHXCOCH3 decompose to give the corresponding acetoxylated ketones, e.g. CH3COCH2OCOCH3. Analogous thallation products have been observed in the reaction of acetone and C2H5COCH3 with thallium (III) iso-butyrate.
Synthesis of Kaempferol-3-0-(3″,4″ -di-O-a-L-rhamnopyranosy)-β-D-galactopyranoside and its Comparison with the Natural Ascaside Isolated from Astragalus caucasicus
Authors: Riess-Maurer Ingrid , Wagner Hildebert , Lipták András
Published: February 2015

Abstract The trisaccharide, 3,4-di-O-(a-L-rhamnopyranosyl)-D-galactose was synthesized using benzyl 2,6-di-O-benzyl-β-D-galactopyranoside as starting compound. Its acetobromo derivative was coupled with 4′,7-di-O-benzyl-kaempferol. The structure of the synthetic kaempferol trioside was characterised by different spectroscopic methods (UV, IR, 1H, 13C NMR and MS). Chromatographic and mass spectrometric comparison of the synthetic product with ascaside precluded their identity.
Isosilychristin, ein neues Flayonolignan aus Silybum marianum L. Gaertn. / Isosilychristin, a New Flavonolignan from Silybum marianum L.Gaertn.
Authors: Kaloga Macki
Published: February 2015

A new flavonolignan, isosilychristin (1), has been isolated from the fruits of Silybum marianum L. Gaertn. Its structure and configuration is elucidated by spectroscopic methods.
Eine neue Darstellungsmethode für Caesiumhydroxid / A New Preparative Method for Cesiumhydroxide
Authors: Jacobs Herbert , Harbrecht Bernd
Published: February 2015

Cesiumhydroxide has been prepared by the reaction of CsOH · H2O with CSNH2 in super-critical ammonia. Thermochemical data for CsOH are given in the range from 100 to 640 K. The x-ray investigation of the compound above 497.5 K shows a sodium chloride type of structure with a = 6,427 (5) Å at 503 K. The lattice constants for the rhombic modification at 298 K are a = 4,350 (3) Å, b = 11,99 (1) Å and c = 4,516 (3) Å. The cell contains four formula units. The structure is of an anti-NaOH type.
Hochdruckreaktionen, XIII [1] Synthese von(—)Cannabidiol unter hohen Drucken / High Pressure Reactions, XIII [1] Synthesis of (—) Cannabidiol at High Pressure
Authors: Kurth Heinz-Jörg , Bieniek Dieter , Körte Friedhelm
Published: February 2015

Cannabidiol 3 has been synthesized under high pressure conditions (7-8 kbar, 150 °C) from Olivetol 1 and trans-p-Menthadien-(2,8)-ol-(1) 2 with 41% yield. The influence of different solvents on the yield has been studied.
Darstellung und Kristallstruktur von Bis-(N-Methylhydroxylamido(1-)-O.N)(N-methyl-N-oxo-dithiocarbamato-O.S)- oxo-molybdän(VI) / Synthesis and Crystal Structure of Bis(N-methylhydroxylamido(1-)-O,N)- (N-methyl-N-oxo-dithiocarbamato-O,S)-oxo-molybdenum(VI)
Authors: Holzbach Wolfgang , Wieghardt Karl , Weiss Johannes
Published: February 2015

The reaction of [MoO2((CH3)HN-O)2] and N-methylhydroxylammoniumchloride in an aqueous suspension with CS2 yields red crystals of the analytical composition MOC4H14N3O4S2. The crystal structure has been determined by single crystal X-ray diffraction analysis. The compound crystallizes in the monoclinic space group P21/c, with cell constants a= 1333.2(3), b = 814.2(2), c = 2179.8(6) pm, β = 105.42(2)°, and Z = 8. The final R-value is 4.5% for 2965 unique reflexions. The structure consists of two crystallographically independent neutral complexes of molybdenum(VI). The geometry about the molybdenum is a distorted pentagonal bipyramid containing a terminal oxygen atom, two N-methylhydroxylamido(1-) ligands coordinated via the O-and N-atoms and an N-methyl-N-oxo-dithiocarbamato(2-) ligand forming a planar five membered ring with the molybdenum(VI) center (O,S-coordination).
S4N4 und seine Derivate: Molekül-und Kristallstruktur von S6N4
2+ (FeCl4
—)2 / S4N4 and its Derivatives: Molecular and Crystal Structure of SeN4
2+ (FeCl4
-)2
Authors: Thewalt Ulf , Burger Maria
Published: February 2015

The reaction of FeCl3 with S4N4 in CH2Cl2 at room temperature yields S6N4
2+(FeCl4
-)2 (A), among other products. Crystal data of A: Space group P21/c, Z = 4, α = 12.090(4), b= 11.745(3), c= 13.918(3) Å, β= 101.25(2)°. In its dimensions and its conformation the S6N4
2+ -cation in A agrees well with the S6N4
2+ -cation in other salts. There exists one close S···Cl contact between each of the S atoms of the central S4 ring in the cation and the neighbouring FeCl4
- anions (3.04 to 3.16 Å; for comparison: the S···Cl van der Waals distance is 3.50 Å).
Elektrochemische Synthesen, VI [1]. Elektrochemische Substitution der VIB-Hexacarbonyle M(CO)6 (M = Cr, Mo, W) / Electrochemical Syntheses, VI [1]. Electrochemical Substitution of VIB-Hexacarbonyls M(CO)6 (M = Cr, Mo, W)
Authors: Grobe Joseph , Zimmermann Heinz
Published: February 2015

The electrochemical substitution of group VIB hexacarbonyls by solvent molecules and/or phosphane ligands is studied in some detail and is found to be a fruitful alternative preparative route to the well-known photochemical reaction.
125Te-NMR-Verschiebungen und Te-P-Kopplungskonstanten von Phosphantelluriden, Tellurophosphanen und Tellurophosphankomplexen / 125Te NMR Shifts and Te-P Coupling Constants of Phosphane Tellurides, Tellurophosphanes, and Tellurophosphane Complexes
Authors: Mont Wolf-Walther du , Kroth Heinz-Jürgen
Published: February 2015

125Te NMR shifts and coupling constants 1J(125Te 31P) of various types of Te-P com-pounds have been measured. 125Te NMR singlets from R3P = Te/PR3 mixtures corroborate the rapid Te migration between tertiary phosphanes. Tellurophosphanes R-Te-PR′2 give well-resolved doublets (R = p·tolyl, trimethylsilyl) or triplets (R = PR'2) due to 1J(125Te 31P) coupling. Coordination of tellurophosphanes to metal carbonyls via the lone pair at phosphorus leads to downfield shifts of the 125Te NMR resonances.
Zum Thermolyseverhalten von 2.2-Dihydro-1.4.2-oxazaphosphol-4-enen, II [1]. Eine einfache Synthese für fluorsubstituierte N-Vinylimidoylchloride / Thermolysis of 2,2-Dihydro-1,4,2-oxazaphosphol-4-enes, II [1]. A Simple Synthesis for Fluorine Substituted N-Vinylimidoyl Chlorides
Authors: Burger Klaus , Goth Herbert , Burgis Eduard
Published: February 2015

3,3-Bis(chlorodifluoromethyl)-2,2,2-trimethoxy-2,2-dihydro-1,4,2-oxazaphosphol-4-enes (2) at room temperature, 3,3-bis(chlorodifluoromethyl)-2,2,2-triphenoxy-2,2-dihydro-1,4,2-oxazaphosphol-4-enes (3) at 140-145 °C undergo cycloelimination of trimethyl, and triphenyl phosphate, respectively, with formation of N-[1-chlorodifluoromethyl-2,2-di-fluoro(vinyl)]-imidoyl chlorides (4) in high yields.
7H-Imidazo[1.2-a]-und -[1.5-a]azepin-7-one / 7H-Imidazo[1,2-a]-and -[1,5-a]azepine-7-ones
Authors: Wolf Ulrich
Published: February 2015

Wittig reactions of imidazole-2- and 4(5)-carboxaldehyde yield the compounds 3 and 4. These vinyl ketones react with N,N-dimethylformamide-dimethylacetal to produce the eneamino-ketones 5 and 6, which are converted into the imidazo-azepine-7-ones (7) and 8.
NOTIZEN. Eine Methode zur Synthese von wasserfreiem Ruthenium(VIII)-oxid / A Method for the Preparation of Anhydrous Ruthenium (VIII) Oxide
Authors: Lößberg Rainer , Müller Ulrich
Published: February 2015

RuO4 can be obtained from Ru metal and ozone at room temperature. This procedure yields pure RuO4 directly, and there are no problems of separation from water as in standard methods of preparation.
Methoxymerkurierung-Demerkurierung von Pheromonen zur Bestimmung der Doppelbindungsposition / Methoxymercuration-Demercuration of Pheromones for Double Bond Position Determination
Authors: Vostrowsky Otto , Michaelis Karl
Published: February 2015

Methoxymercuration-demercuration, Pheromones Methoxymercuration-demercuration of alkenyl acetates and alkenols yields methoxyderivatives which were analysed by mass spectrometry to determine the original double bond position.
Zur Kenntnis des Bariumthioantimonats(III) Ba8Sb6S17 / On Bariumthioantimonate(III) Ba8Sb6S17
Authors: Dörrscheidt Wolfgang , Schäfer Herbert
Published: February 2015

Bariumthioantimonate(III), Crystal Structure Ba8Sb6S17, prepared by fusion of the binary sulfides at 1120 K, crystallizes in the mono-clinic system (space group:P2/c) with a= 1141 ± 1 pm, b = 1373 ± 1 pm, c = 2253 ± 2 pm, β = 90.94 ± 0.05°. In the structure there are isolated distorted SbS3
3- -trigonal pyramids (ψ-tetrahedra) and hitherto unknown Sb3S8
7--units consisting of a central SbS4-ψ-trigonal bipyramid connected by the common axial S-atoms with two further SbS3
3- groups.
Reactions of Biscyclopentadienyl Vanadium with NO and XNO (X = Cl OR Br)
Authors: Morán M. , Gayoso M.
Published: February 2015

The reactions of (η-C5H5)2V with NO and XNO (X = CL or Br) lead to the formation of [η-C5H5V(NO)2]2 and (η-C5H5)2VX(NO) (X = CL or Br) respectively. The compounds have been characterized by elemental analysis, magnetic moments and IR and EPR spectra.
Two-Dimensional (2D-J) NMR Spectroscopy for Analysis of Isomers and Heterocouplings
Authors: Benn Reinhard , Riemer Werner
Published: February 2015

The use of two-dimensional NMR spectroscopy (2D-J) for the identification of isomers and heterocouplings is demonstrated. The routine application of this new method to practical NMR problems is discussed.
The Fluctional Behaviour of the P7 Trianion -A Molecular Orbital Study
Authors: Böhm Michael C. , Gleiter Rolf
Published: February 2015

The degenerate rearrangement of P7
3- has been studied by means of the MINDO/3 method. The calculated enthalpy of activation (⊿H≠ = 59.12 kJ/mol) is in good agreement with results from 31P NMR studies at different temperatures. The bond switching process starts with a bond rupture leading to a transition state with C2v symmetry. Possible rearrangements in P6S2-and P6CH2-are discussed.
New Phospha(III)azenes / New Phospha(III)azenes
Authors: Scherer Otto J. , Conrad Herbert
Published: February 2015

The interaction of RR'N-PCl2 (1) with LiNR"SiMe3 gives monomeric phospha(IH)-azenes RR'N-P=N-R"; R = R"=i-C3H7, R'= (CH3)3C (3a); R=i-C3H7,R'=R" = (CH3)3C (3b); R = i-C3H7, R' = (CH3)3C, R"=(CH3)3Si (3c) as distillable liquids. 3a adds PCl3 with formation of RR'N-PCl-NR-PCl2, R = i-C3H7, R'=(CH3)3C (6).
Tl4Ge4Se10, ein Thallium(1)selenogermanat mit adamantananalogem Anion [Ge4Se10]4- / Tl4Ge4Se10, a Thallium(I) Selenogermanate with the Adamantane-Like Anion [Ge4Se10]4-
Authors: Eulenberger Günther
Published: February 2015

Tl4Ge4Se10 crystallizes in space group C2/c with a = 15.602(6), b = 15.549(5), c = 9.052(3) Å, β - 107.10(3)° and Z = 4. The compound was prepared by fusion of a stoichiometric mixture of Tl2Se and GeSe2. The crystal structure is characterized by adamantane-like anions [Ge4Se10]4- and Tl+ cations. Tl4Ge4Se10 is iso-structural with Tl4Ge4S10 [1].
Beiträge zur Chemie des Phosphors, 103 [1, 2]. Tri-tert-butyl-diphosphaarsa-cyclopropan, (t-BUP)2 (t-BuAs) / Contributions to the Chemistry of Phosphorus, 103 [1, 2]. Tri-tert-butyl-diphosphaarsa-cyclopropane, (t-BuP)2(t-BuAs)
Authors: Baudler Marianne , Klautke Siegfried
Published: February 2015

The first three-membered P2AS heterocycle, tri-tert-butyl-diphosphaarsa-cyclopropane (tri-tert-butyl-diphosphaarsirane) (1) was synthesized by [2+1] cyclocondensation of K(t-Bu)P-P(t-Bu)K with t-BuAsCl2 in n-pentane at - 78 °C. Tetra-tert-butyl-1,2-di-phospha-3,4-diarsa-cyclobutane (2), tetra-tert-butyl-triphosphaarsa-cyclobutane (3) as well as (t-BuP)4 and five-membered cycloarsaphosphanes are also formed. The diphospha-arsa-cyclopropane 1 could be isolated in a pure state. It forms two diastereomers, of which the isomer with trans-orionted tert-butyl groups at the phosphorus atoms is the most stable. The 31P NMR parameters of the four-membered cycloarsaphosphanes 2 and 8 are reported
(MePNMe)4 · MeI und (MePNMe)4 · 2 MeI, ein Cyclotetra(λ3λ3λ3λ5-) und ein Cyclotetra(λ3λ5λ3λ5-phosphazan) / (MePNMe)4 · MeI and (MePNMe)4 · 2 MeI, a Cyclotetra(λ3λ3λ3λ5-) and a Cyclotetra(λ3λ5λ3λ5-phosphazane)
Authors: Zeiß Werner , Kuhn Tino
Published: February 2015

Cyclotetraphosphazanes (2) with three PIII and one Pv, and (3) with two PIII and Pv atoms are prepared from 1 with methyl iodide. NMR spectra of 2 are compared with those of the recently prepared [1] 4. The crystal structure of 3 shows the molecule to have a crystallographic inversion centre. Thus cis-trans isomerisation must have taken place during the working up procedure. Alkylation has severe consequences on bond distances and bond angles of the cyclotetraphosphazane ring system, in contrast to M(CO)5 complexation at the same positions as shown in a similar case recently [8]
Chemie polyfunktioneller Liganden, 64 [1]. Über Hydridoiridium(III)-Komplexe des N.N-Bis(diphenylphosphino)-p-tolylamiii Chemistry of Polyfunctional Ligands, 64 [1]. On Hydridoiridium(III) Complexes of N,N-Bis(diphenylphosphino)-p-tolylamine
Authors: Ellermann Jochen , Mader Leo , Geibel Kurt
Published: February 2015

H2 reacts with [Ir{(Ph2P)2N-p-C6H4CH3}2]Cl · 3 C6H6 (1) to give cis-[Ir(H)2{(Ph2P)2N-p-C6H4CH3}2]Cl · CH2Cl2 (2a). By reaction of 2a with NaBPh4 cis-[Ir(H)2{(Ph2P)2N-p-C6H4CH3}2]BPh4 (2 b) is obtained. Refluxing of 2a in CH2Cl2 yields trans-[lr(H)2{(Ph2P)2N-p-C6H4CH3}2]Cl · 1/2 CH2Cl2 (3a), which undegoes metatheses with NaBPh4 to trans-[Ir(H)2{(Ph2P)2N-p-C6H4CH3}2]BPh4 (3b). 3a is also formed by refluxing of 1 in methanol in the presence of oxygen. Oxidative addition of HCl to 1 and reaction with NaBPh4 yields trans-[Ir(H)(Cl){(Ph2P)2N-p-C6H4CH3}2]BPh4 (4b). The new compounds are characterised by their IR, Raman, 31P{1H} PFT and 1H NMR Spectra
Versuche zur Rhodium(I)-katalysierten asymmetrischen Hydrierung von α-Acetamidozimtsäure mit monomeren und polymeren Aminophosphinen / Rhodium (I) Catalyzed Asymmetric Hydrogenation of α-Acetamido Cinnamic Acid with Monomeric and Polymeric Aminophosphines
Authors: Nagel Ulrich , Menzel Hartmut , Lednor Peter W. , Beck Wolfgang , Guyot Alain , Bartholin Michel
Published: February 2015

An optically active 1-phosphino-2-aminopropane, prepared from ephedrine, has been used for the Rh(I) catalyzed asymmetric hydrogenation of α-acetamido cinnamic acid. Optical yields up to 77 percent were obtained. Low stereoselectivity has been found using 1,4-bis(diphenylphosphino)-2,5-dibenzylpiperazine and a polystyrene bound bisdiphenyl-phosphine, obtained from phenylalanine. The preparation of optically active piperazines from α-amino acids is reported
Reaktionen mesoionischer Fünfringheterocyclen mit o-chinoiden Verbindungen, IV [1]. Mono- und tricyclische 1.3-Thiazolium-4-olate, 1.3-Dithiolylium-4-olate / Reactions of Mesoionic Five-Membered Heterocycles with o-Quinonoid Compounds, IV [1]. Mono- and Tricyclic 1,3-Thiazolium-4-olates, 1,3-Dithiolylium-4-olates
Authors: Friedrichsen Willy , Schröer Wolf-D. , Schwarz Ingo , Böttcher Andreas
Published: February 2015

Monocyclic 1,3thiazolium-4-olates (10) react with o-quinonoid compounds to give [π4 + π4] cycloadducts (12, 13); tricyclic 1,3-thiazolium-4-olates (14, 15) yield compounds (17, 18, 19, 20) which can formally be derived from a ketene tautomer (C). 1,3-Dithiolylium-4-olates are borderline cases; both [π4+ π2] (32) and [π4 + π4] adducts (34) were obtained
Reaktionen mesoionischer Fünfringheterocyclen mit o-chinoiden Verbindungen, V [1, 2]. 1.3-Oxazolium-5-olate und 1.3-Thiazolium-5-olate / Reactions of Five-Membered Mesoionic Heterocycles with o-Quinonoid Compounds, V [1, 2] 1,3-Oxazolium-5-olates and 1,3-Thiazolium-5-olates
Authors: Friedrichsen Willy , Schwarz Ingo , Epe Bernd , Hesse Karl-Friedrich
Published: February 2015

1,3-Oxazolium-5-olates (1) 1,3-thiazolium-5-olates (11) react with o-benzoquinones (3) and α-naphthoquinone to give adducts (4, 5, 6, 15) which can formally be derived from ketone valence tautomers of 1 and 11. 9,10-Phenanthrenequinone and 1 a yield a compound (10) which possibly results from an initially formed [π4 + π4] adduct (7) with subsequent loss of CO2. Consistent with this view is a product (14) of the reaction between 9,10-phenanthrenequinone and 11. The structure of 14 has been determined by X-ray crystallography
Cycloadditionen mit o-Benzochinon-diiminen, VI [1]. Reaktionen von Diarylbenzo[c]furanen mit o-Benzochinon-diiminen. Stabile Sessel- und Wannenkonformere in der 5.6.11.12-Tetrahydrodibenzo [b.f] [1.4] diazocinreihe / Cycloadditions with o-Benzoquinone-diimines, VI [1]. Reactions of 1,3-Diarylbenzo[c]furans with o-Benzoquinone-diimines. Stable Chair and Boat Conformers in the 5,6,11,12-Tetrahydrodibenzo[b,f][1,4]diazocin Series
Authors: Friedrichsen Willy , Röhe Meike , Debaerdemaeker Tony
Published: February 2015

N,N′-Diarylsulfonyl- and N,N′-Dibenzoyl-o-benzoquinone-diimines (4) react remarkably easy with 1,3-diarylbenzo[c]furans (5) to give [π4 + π4] cycloadducts (6). In one case (6a) the chair and boat conformer of this type of adduct could be isolated and the conformations clarified by X-ray crystallography. On heating compounds 6 can rearrange intramolecularly to give 2H-benzimidazoles (7)
Could Hydrogen Peroxide Photolysis Occur in the Absence of Transition Metals ?
Authors: Luňák Stanislav , Vepřek-Šiška Josef
Published: February 2015

Quantum yields of hydrogen peroxide photolysis increase with the square root of concentration of added Cu(II). The cupric ions are photo-catalytically active already at trace concentrations (10-7), i.e., at the concentrations present in any real reaction system. Hydrogen peroxide photolysis is completely suppressed on addition of complexing agents such as EDTA. It is believed that no hydrogen peroxide photolysis would occur in complete absence of photo-catalytically active transition metal ions
Die Stabilisierung von Tris(hydrazino)phosphan durch Komplexbildung / The Stabilisation of Tris(hydrazino)phosphane by Complex Formation
Authors: Nöth Heinrich , Thorn Volker
Published: February 2015

The solvolysis of (CO)5CrPCl3 with N2H4 or H2N-N(CH3)2 yields (CO)5CrP(NH-NH2)3 and (CO)5CrP[NH-N(CH3)2]3 respectively containing the hitherto unknown and unstable ligands P(NH-NH2)3 and P[NH-N(CH3)2]3. Their constitution is derived from spectroscopic data.
Nitrido-azido-Komplexe des Molybdäns(VI) Synthese und Kristallstruktur von MoN(N3)3(NC5H5) / Nitrido Azido Complexes of Molybdenum (VI) Synthesis and Crystal Structure of MoN(N3)3(NC5H5)
Authors: Schweda Eberhard , Strähle Joachim
Published: February 2015

The explosive nitrido azido complexes MoN(N3)Cl2 · py and MoN(N3)3py are prepared by the reaction of MoCl4(py)2 with (CH3)3SiN3 in 1,2-dichloroethane. Both compounds hydrolyze quickly in moist air. After separation of the insoluble, black MoN(N3)Cl2 · py from the solution of MoN(N3)3py, the latter can be obtained in form of monoclinic, red crystals of the space group C2/c. Its structure consists of monomeric complexes, wherein the Mo atom has a square pyramidal coordination. The nitrido ligand occupies the apex and forms a strong multiple bond of 163.4 pm to the Mo atom. σ-Bonds of different strength exist between the Mo atom and the basal ligands: MO-N3 - 204.3 pm; Mo-py = 225.8 pm. The α-N atoms of the azido groups are sp2 hybridized, with their lone pair pointing away from the nitrido ligand. The pyridine ligand forms an angle of 61.6° to the basal plane of the coordination polyhedron.