bluuebunny/crossref_metadata_2025 huggingface dataset:
Darstellung und Struktur von S3N3O2Cl / Preparation and Structure of S3N3O2Cl
Authors: Roesky Herbert W. , Emmert Ralf , Noltemeyer Mathias , Sheldrick George M.
Published: February 2015

S3N3O2Cl (2) can be isolated as a decomposition product of S3N3O2Cl2 (1) in methylene chloride. Crystals of 2 are monoclinic, space group C2/c, with a - 1729.0(9), b = 670.7(4), c = 1201.4(7) pm, ft = 114.05(3)°. The structure was refined to R = 0.035 for 722 diffractometer data. 2 is the first compound containing a S3N3-ring with three differently coordinated sulfur atoms.
Synthese und Kristallstrukturanalyse von Undecacarbonyl- (μ-trifluormethylisocyanid)trieisen, Fe3(μ-CNCF3)(CO)11 / Synthesis and Crystal Structure Determination of Undecacarbonyl(μ-trifluoromethylisocyanide)triiron, Fe3(μ-CNCF3)(CO)11
Authors: Brüdgam Irene , Hartl Hans , Lentz Dieter
Published: February 2015

The unstable trifluorom ethylisocyanide can be stabilized on the Fe3(CO)11 framework. Infrared data suggest that the isocyanide ligand occupies bridging positions in the solid state and in solution. This fact has been confirmed by the crystal structure analysis and by 13C NMR measurements.
Ca3AlSb3 und Ca5Al2Bi6, zwei neue Zintlphasen mit kettenförmigen Anionen / New Zintl Phases with Chain Anions: On Ca3AlSb3 and Ca5Al2Bi6
Authors: Cordier Gerhard , Schäfer Herbert , Stelter Michael
Published: February 2015

The new compound Ca3AlSb3 crystallizes in the orthorhombic system (space group Pnma (No. 62)) with lattice constants

a = 1283.5(5) pm, b = 448.9(2) pm , c = 1428.2(5) pm

In the structure there are AlSb4 tetrahedra connected by common corners to form chains. The new compound Ca5Al2Bi6 crystallizes in the orthorhombic system, too (space group Pbam (No. 55)) with lattice constants

a = 2333.3(8) pm, b = 758.2(3) pm, c = 452.9(2) pm

AlBi4 tetrahedra are connected by common corners and Bi2 groups to form double chains. Both compounds are classified as Zintl phases.
Röntgenstrukturuntersuchungen an Verbindungen mit P—NH—P-Gerüst / X-Ray Structural Studies on Compounds with a P —NH-P Backbone
Authors: Nöth Heinrich , Fluck Ekkehard
Published: February 2015

The structures of four compounds containing the P-NH-P unit have been determined by X-ray methods in order to detect prototropism. Ph2P-NH-PPh2 in the solid state is indeed a bis(diphenylphosphino)amin having C2 molecular symmetry. Its bisborane(3) ad­duct possesses the structure Ph2P(BH3)-NH-P(BH3)Ph2 with the BH3 -groups in transoid position. The P-NH-P unit is also observed in (PhO)2P(O)-NH-P(O)(OPh)2 and (PhO)2P(O)-NH-P(O)(C2H5)2. These two compounds show weak intermolecular hydrogen bonding in the solid state to the oxygen atom of a phosphoryl group. The PN bond distances depend on the group X bonded to phosphorus and decrease in the series with X = BH3 > S > O, e.g. with the electron withdrawing ability of X.
Struktur und Schwingungsspektrum der Heteropolyverbindung K13[KP2W20O72] · xH2O / Structure and Vibrational Spectrum of the Heteropoly Compound K13[KP2W20O72] · xH2O
Authors: Fuchs Joachim , Palm Rosemarie
Published: February 2015

The title compound crystallizes monoclinicly in the space group P21/c with lattice parameters a = 13.522 Å, b = 22.379 Å, c = 15.071 Å und β = 95.95°. In the polyanion two α-PW9O34 moieties are bridged by two octahedral WO6 units. A potassium ion in the central cavity is surrounded by eight oxygen atoms of the polyanion in hexagonal bipyramidal coordination. - The vibration spectrum of the solid and its aqueous solution are discussed.
Zwei neue Tetraphosphor-trichalkogeno-diiodide α′-P4Se3I2 und α′-P4S3I2 / Two New Tetraphosphorus-trichalcogeno-diiodies α′-P4Se3I2 and α′-P4S3I2
Authors: Blachnik R. , Kurz G. , Wickel U.
Published: February 2015

α′-P4Se3I2 and α′-P4S3I2 were prepared by the reaction of P4S3 (P4Se3) with I2 in the molten state. The structure of α′-P4Se3I2 was determined. The compound crystallizes in the tetragonal space group I4̄2d with a - 1200.5(2) pm, c = 1518.8(4) pm, and eight molecules per unit cell. The structure was refined with 814 of 1402 observed reflections to a conventional residual of R = 0.045. One half of a molecule is forming the asymmetric unit. α′-P4S3l2 is isotypic with the lattice parameters a = 1182.2(2) pm and c = 1496.8(4) pm. 31P NMR data confirm that both modifica­tions have the same bicyclic molecular structure in solution as in the solid state and form an AA′BB′ system. Evidence is presented that the α-isomer is stabilized by the formation of two additional weak P-X bonds in this molecule.
Reactions of (SCN)2 with SnX4(X = Br, I)
Authors: Tudela D. , Fernandez V. , Tornero J. D.
Published: February 2015

From the reaction between (SCN)2 and Snl4 a compound is formed the formula of which is ISn(NCS)3 · I2, in which I2 molecules form charge-transfer complexes with thiocyanate groups. ISn(NCS)3 can be isolated from this compound. Both compounds were characterised by means of elemental analyses and UV-visible, IR and 119Sn Mossbauer spectra, and a polymer structure with thiocyanate bridges was deduced. The equilibrium constant was calculated for the reaction: ISn(NCS)3 · I2(solid)+CS2 ⇌ ISn(NCS)3(solid) + I2(solution) K = 2.2±0.3 x 10-3 mol l-1 and it was found that the two solid compounds form a single phase. SnBr4 forms an unstable addition compound with (SCN)2, which decomposes even below 0 °C.
ESCA-Untersuchungen über die Ladungsverteilung und den Bindungszustand der λ3- und λ5-Phosphorine / ESCA-Studies of the Charge Distribution and Boding of λ3- and λ5-Phosphorines
Authors: Knecht Josef
Published: February 2015

The ESCA -spectroscopic examination of λ3- and λ5-phosphorines supports the theory, that these compounds are to be described as aromatic compounds and as cyclic phosphonium-ylides, respectively. Contrary to simple electronegativity considerations, the phosphorus atom in the λ3- phosphorines is nearly neutral and not positively charged.
Das Reduktionsverhalten von Pentacarbonylpyridin-Komplexen des Chroms, Molybdäns und Wolframs / The Reduction Behaviour of Pentacarbonylpyridinechromium, -molybdenum and -tungsten Complexes
Authors: Kaim Wolfgang
Published: February 2015

The reduction of group VIB metal pentacarbonyl complexes and of iodomethylates of 4- trimethylsilyl-, 4-acetyl- and 4-cyanopyridine has been investigated. Informations on the dissociation of the complexes and on the potential and reversibility of the one-electron reduction were obtained by cyclic voltammetry in DMF, whereas electron spin resonance (ESR) studies of the primary reduction products in the 4-acetylpyridine series revealed the distribution of the unpaired electron. The results suggest that the lowest unoccupied molecular orbital (LUMO) is a ligand centered π*-orbital in the 4-acetyl- and 4-cyanopyridine complexes, thus confirming assignments from photochemistry. The results allow an assessment of both N-coordination and substituent effects at the heterocyclic ligand.
Synthesis and Characterization of Some Transition Metal Complexes of Arylidene Salicyloyl and Benzoyl Hydrazones
Authors: Temerk Y. M. , Ibrahim S. A. , Kamal M. M.
Published: February 2015

Complexes of arylidene salicyloyl- and benzoyl-hydrazones with the 3d metal ions, Cr(III), Mn(II), Fe(III), Co(II), Ni(II) and Cu(II), have been prepared using 2:1 ligand to metal ion ratio. Characterization of the isolated solids was accomplished by IR and electronic spectra, elemental analysis, and molar conductivity measurements. It is concluded that the two Schiff bases function as neutral bidentate ligands and the complexes formed assume a distorted octahedral geometry.
Über das 2.3.6-TriacetyI-5-ethyltoluol und das 2.3.5.6-Tetraacetyltoluol / On the 2,3,6-Triacetyl-5-ethyltoluene and 2,3,5,6-Tetraacetyltoluene
Authors: Riemschneider R. , Hennig K.
Published: February 2015

2,3,6-Triacetyl-5-ethyl-toluene and 2 ,3 ,5 ,6 -tetraacetyl-toluene were prepared by permanganate oxidation of 2,6-diacetyl-3,5-diethyl-toluene. NMR and MS data are given.
Die Kristallstrukturen von PPh4[WOCl4], (PPh4)2[WOCl5] · 2CH2CI2 und (PPh4)2[ReOCl5] · 2CH2Cl2 / The Crystal Structures of PPh4[WOCl4], (PPh4)2[WOCl5] · 2CH2CI2 and (PPh4)2[ReOCl5] · 2CH2Cl2
Authors: Fenske Dieter , Stahl Karlheinz , Hey Evamarie , Dehnicke Kurt
Published: February 2015

Both tungsten compounds are formed by reaction of water and oxygen with the acetylene complex PPh4[WCl5(Ph - C ≡ C - C (Br) = C(Br) -Ph)] in CH2Cl2 solutions, and in the presence of PPh4Cl. PPh4[WOCl4] crystallizes in the tetragonal space group P4/n, with two formula units in the unit cell of dimensions a = b = 1269, c = 760 pm at -110 °C (1416 observed in dependent reflexions, R = 0 .054). The [WOCl4]⊖ ion forms a tetragonal pyramid with the oxygen ligand in axial position and a tungsten -oxygen distance of 168 pm. (PPh4)2 [WOCl5 · 2CH2Cl2 crystallizes in the tricline space group P 1̄, with one formula unit per unit cell with a = 1011, b = 1113, c = 1240 pm, α = 70.3°, β = 79.4°, γ = 80.9° at - 110 °C (3781 observed in dependent reflexions, R = 0 .087). The structure contains [WOCl5]2
⊖ an ions where the oxygen atom and the chlorine atom in transposition are disordered. (PPh4)2[ReOCl5] · 2CH2Cl2 is formed by the reaction of ReCl5 with PPh4Cl in the presence of water. The compound is isotypic with the corresponding tungsten complex (space group P 1̄, Z = 1, a = 1006, b = 1109, c = 1239 pm , α = 7 0.5°, β = 79.6°, γ = 80.9° at -110 °C; 5436 observed in dependent reflexions R = 0 .050).
Kristallstruktur und spektroskopische Untersuchung von Mg(GeMe3)2 · 2 DME / Crystal Structure and Spectroscopic Study of Mg(GeMe3)2 · 2 DME
Authors: Rösch Lutz , Krüger Carl , Chiang A .-P.
Published: February 2015

Mg(GeMe3)2 · 2 DME is synthesized by reaction of Hg(GeMe3)2 with magnesium in 1 ,2 -- dimethoxyethane. The X-ray structure, IR, Raman, 1H NMR , and 13C NMR spectra of this first organogermyl magnesium compound are reported.
The Crystal Structure of [(Quinoline)2CuI]2 · CH3CN
Authors: Hiller Wolfgang
Published: February 2015

The unit Cell of [(quinoline)2CuI]2 · CH3CN is monoclinic, space group C2/c, with a = 1974.0(4), b = 764 .4 (2), c = 2521 .7 (4) pm, β = 112.64(6)° and Z = 4. The structure consists of discrete dimers with a strictly planar Cu2I2 moiety . Each copper atom is coordinated to two bridging iodine atoms and two terminal quinoline ligands. The unit cell contains four acetonitrile molecules.
Ba3Si4P6, eine neue Zintlphase mit vernetzten Si4P5-Käfigen / On Ba3Si4P6, a New Zintl Phase with Connected Si4P5 Cages
Authors: Eisenmann Brigitte , Jordan Hanna , Schäfer Herbert
Published: February 2015

The new compound Ba3Si4P6 crystallizes in the monoclinic system, space group P21/m(No.11) with the lattice constants a = 1153.7(3) pm, b = 728.1(2) pm, c=752.7(2) pm, β = 99.41(5)°. Si4P5 cages are connected by Si chains and P bridges to corrugated two-dimensional nets between which the Ba ions are located. The compound is a Zintl phase and therefore belongs to the valence compounds.
Formen des Diphenylgermaniumoxids(Ph2GeO)x, x = 3, 4, n / Phases of Diphenylgermanium Oxide(Ph2GeO)x, x = 3, 4, n
Authors: Roß Ludwig , Dräger Martin
Published: February 2015

Diphenylgermanium oxide can be obtained trimeric (6 -membered ring, monoclinic crystals), tetrameric (8 -membered ring, monoclinic and tetragonal crystals and monoclinic with half a mole of crystal ethanol) and polymeric with terminating hydroxy groups. Transitions are investigated by thermal analysis, mass spectra and 13C NMR spectra. The vibrational spectra (I. R . and Raman) of the forms are discussed . The crystal structure of the monoclinic (Ph :GeO)4 has been determined and refined to R = 0.051. The symmetry of the molecule is near to S4 (distances Ge - O 174.7 - 176.2, Ge - C 190.0 - 194.6 pm, angles Ge - O - Ge 131.2 - 136.9, O - Ge - O 107.8 -110.3 °).
Zur Synthese von Tetramethyldibismutan und dessen Spaltung zu Bis(dimethylbismut)oxid oder -sulfid bzw. Phenyldimethylbismutan / A Synthesis of Tetramethyldibismuthane and its Cleavage to Bis(dimethylbismuth)oxide or Sulfide and Phenyldimethylbismuthane, Respectively
Authors: Wieber Markus , Sauer Ingbert
Published: February 2015

Tetramethyldibismuthane, Me4Bi2 was prepared in high yields by reducing Me2BiBr with sodium in liquid ammonia. The compound reacts quantitatively with equimolar amounts of oxygen or sulfur to yield the corresponding (Me2Bi)2O and (Me2Bi)2S. By cleavage of Me4Bi2 with PhLi, PhBiMe2 was obtained ; the latter is also available in better yields by the reaction of Me2BiBr with PhLi.
Beiträge zur Chemie der Trifluormethylselen(II)- und -selen(IV)-Verbindungen / Advances in Trifluoromethylselenium (II)- and -selenium (IV)-Chemistry
Authors: Haas Alois , Tebbe Klaus
Published: February 2015

Fluorination of CF3SeCl with AgF leadsto CF3Se(O)OH and CF3SeSeCF3 after reactions of the primary products with glass.Condensations of (CF3S)2NH and [(CH3)3Si]2NH with CF3SeCl gave CF3SeN(SCF3)2, and [(CH3)3Si]2NSeCF3, (CF3Se)2NSi(CH3)3, CF3SeN(H)Si(CH3)3, respectively. The reaction of FC(O)SCl with Hg(SeCF3)2 gave besides FC(O)SSeCF3 in smaller quantities also CF3SeSSeCF3. When a mixture of (CF3Se)2NH and Cl3S3N3 is heated to 50°C, CF3SeN=S=NSeCF3 is formed. The oxydation of CF3SeCF2X with ClF or m-chloroperbenzoic-acid gave CF3Se(O)CF2X (X = F, Cl). Spectroscopical data of the substances are provided.
Derivate des 1.3-BenzdioxoIs, 52 Darstellung und Reaktionen von 1.3-Dioxolo[4.5-b]phenazinen / Derivatives of 1,3-Benzdioxoles, 52 Preparation and Reactions of 1,3-Dioxolo[4,5-b]phenazines
Authors: Dallacker Franz , Wagner Alfred
Published: February 2015

We describe the preparation of the 1,3-dioxolo[4,5-b]phenazines 4 a -p formed by ferric chloride oxidation of the corresponding 2,2′-diaminodiphenylamines. They are obtained by condensing the o-nitrohalogenbenzenes 1 a -g with o-nitroanilines 2 a-i and reduction of the resulting 2,2′-dinitrodiphenylamines 3 a -p with H2/Pd.
Discotic Mesophases of the Hexakis(alkylsulfono)benzene Series: Characterization by Differential Scanning Calorimetry, Optical Microscopy and Nuclear Magnetic Resonance Spectroscopy
Authors: Praefcke K. , Poules W. , Scheuble B. , Poupko R. , Luz Z.
Published: February 2015

Members of the Hexakis(alkylsulfono)benzene series 4, containing 7 to 15 carbon atoms per alkyl chain (4 c-k), exhibit one and possibly several liquid crystalline discotic mesophases. The mesophases are uniaxial and most probably have a columnar structure. Their anisotropic magnetic susceptibility is negative and in sufficiently strong magnetic fields they align with the director perpendicular to the field direction. Deuterium NMR spectra of C6D6 dissolved in the mesophases exhibit quadrupolar splittings which are strongly temperature dependent. In analogy with the conventional discotics this suggests the presence of multiple solvation sites for solute molecules.
Elektrochemische Synthesen, X Katalytische Anwendung elektrochemischer Systeme: Cyclooligomerisation von Acetylen / Electrochemical Syntheses, X Catalytic Application of Electrochemical Systems: Cyclooligomerization of Acetylene
Authors: Grobe Joseph , Schneider Bernd Heinz , Zimmermann Heinz
Published: February 2015

Following known procedures for the preparation of nickel complexes as precursors to active contact species for the cyclooligomerization of acetylene we report the electrochemical formation of Ni(CO)2(PPh3)2 and its use in a one-pot trimerization of acetylene to benzene. Further investigations demonstrate the possibility to simultaneously produce and use as catalysts active nickel solvates generated from nickel anodes for the cyclization of acetylene to benzene and/or cyclooctatetraene.
Der 2-Trichlormethyl-2-propyl — Rest als Phosphatschutz in der Oligonukleotidsynthese / The 2-Trichloromethyl-2-propyl Group as a Protecting Group in Oligonucleotide Synthesis
Authors: Schneiderwind-Stöcklein Ruth G. K. , Ugi Ivar
Published: February 2015

The synthesis of pure TCB-dichlorophosphite and di-TCB-monochlorophosphite are described, as well as the formation of the di-triazolide from TCB-dichlorophosphite and its use in the preparation of a dinucleotide derivative.
Ritter Reaction on Terpenoids, I Stereospecific Preparation of (1 S,5 R,8 R) and (1 R ,5 S,8 S) 8-Acetamido-2,4,4,8-tetramethyl-3-aza-bicyclo[3.3.1]non-2-ene Perchlorate
Authors: Caram J. , Martins M. E. , Marschoff C. M. , Cafferata L. F. R. , Gros E. G.
Published: February 2015

Treament of ( + )limonene with diluted perchloric acid in acetonitrile solution afforded (1 S ,5 R ,8 R ) 8-acetamido-2,4,4.8-tetramethyl-3-aza-bicyclo[3.3.1]non-2-ene perchlorate while the same reaction on ( - )β-pinene produced the (1 R ,5 S ,8 S ) enantiomer, and terpinolene gave the racemic mixture. The structure of the product is proposed on basis of its physical and spectroscopic (IR, 1H and 13C NMR, MS) properties and its formation involves a Ritter reaction between the monoterpene and acetonitrile.
1,4-Dithia-2,6-diaza-3,5-diborinane: Ein neues B–N–S-Ringsystem/ 1.4-Dithia-2.6-diaza-3,5-diborinanes: A Novel B – N –S-Ringsystem
Authors: Habben Carl , Meller Anton
Published: February 2015

The novel 1,4-dithia-2,6-diaza-3,5-diborinane ring system results from the reaction of 3,5- dialkyl- (or di-sec.amino-) substituted 1,2,4-trithia-3,5-diborolanes with 1.3-disubstituted sulfurdiimides by replacement of the disulfane bridge. Upon treatment with azomethines, 3,5-dibromo- 1.2.4-trithia-3,5-diborolane gives 3,5-dibromo-1,2-dithia-4-aza-5-diborolidines by substitution of the sulfur atom in position 4. 1H , 11B , 13C, 29Si NMR and mass spectra are reported and discussed.
(η2-Alken)organyIruthenium(II)-KompIexe und Ethyleninsertion in Phenyl-Ruthenium-Bindungen/ (η2-A lkene)organylruthenium (II) Complexes and Ethylene Insertion into Phenyl-Ruthenium Bonds
Authors: Lehmkuhl Herbert , Grundke Jürgen , Schroth Gerhard , Benn Reinhard
Published: February 2015

The reaction of the alkyl-bis(triphenylphosphine)ruthenium complexes 1-3 with ethylene (50 -150 bar) at 70 -100 °C proceeds by initial phosphine dissociation to give the η2-ethylenealkylruthenium compounds 6 -8 . The phenyl-ruthenium complex 4 reacts, under these conditions, by ethylene insertion into the Ph-Ru bond. Subsequent Ru-βH-elimination gives the diastereomeric η2 -styrene-hydrido-ruthenium compounds 10a and b. At low ethylene pressure (5 - 8 bar), 1 - 3 react mainly by orthometallation of a phosphinehenyl group followed by rapid ethylene insertion into the resulting Ph-Ru bond and Ru-βH-elimination to give the diastereomeric complexes 9a and b.
Tris(phosphan)-Nickel(0)-Ethen-Komplexe (dmpe)(PR3)Ni(C2H4). Molekülstruktur des (dmpe)(PØ3 )Ni(C2H4)/ Tris(phosphane)-nickel(0)-ethene Complexes (dmpe)(PR3)Ni(C2H4). Molecular Structure of (dmpe)(PO3)Ni(C2H4)
Authors: Pörschke Klaus R. , Mynott Richard , Krüger Carl , Romão M. J.
Published: February 2015

Synthesis and properties of tris(phosphane)(ethene)nickel(0) complexes (dmpe)(PR3)Ni(C2H4) (R = CH3(4), c-C6H11(5), and C6H5 (6)) are reported. In solution. 4-6 are thermolabile and undergo ligand exchange reactions affording tetrakis(phosphane)nickel(0 ) and bis(phosphane)- (ethene)nickel(0) complexes. 1H, 13C, and 31P NMR data of 4-6 confirm the tetrahedral geometry around nickel. For 6 , the crystal and molecular structure has been determined by X-ray crystallography.
Kristall- und Molekülstruktur von As2P2S7/ Crystal and Molecular Structure of As2P2S7
Authors: Hönle Wolfgang , Wibbelmann Claus , Brockner Wolfgang
Published: February 2015

The crystal and molecular structures of As2P2S7 has been determined by single crystal X-ray diffraction (space group V 21/c; Z = 4; a = 1174.6(16) pm; b = 823.9(7) pm; c = 1140.1(10) pm; β - 94.43(9)°; R = 0.073. The molecule is isosteric to P4S7 and possesses C2v symmetry. Mean bond lengths are: d (As-As) = 250.9 pm; d (As-S ) = 225.7 pm; d(P - S) = 208.3 pm and d(P = S) = 193.2 pm. The observed As -As bond length agrees well with spectroscopic results
Reaktionen von Dithiooxamid mit Chlormethylsilanen/ Reactions of Dithiooxamide with Chlormethylsilanes
Authors: Roesky Herbert W. , Hofmann Hartmut
Published: February 2015

Reactions of dithiooxamide with chloromethylsilanes are leading to different kinds of products. Depending on the conditions and the reaction pathways N,N′-silylsubstituted dithiooxamides, cyclic dithiooxamides and a dithiooximide can be obtained. All products are sensitive to moisture.
Darstellung und Schwingungsspektren von Fluoro-Chloro-Osmaten(IV) einschließlich der Stereoisomeren/ Preparation and Vibrational Spectra of Fluoro-Chloro-Osmates(IV) Including Stereoisomers
Authors: Preetz W. , Ruf D. , Tensfeldt D.
Published: February 2015

The stepwise replacement of ligands in [OsCl6]2- by oxidation with BrF3 generates the mixed complexes [OsFnCl6-n]2-, n = 1 - 5, of which the species with n = 2,3,4 are cw-configurated. Due to the stronger trans-effect of Cl compared to F on treatment of [OsF5Cl]2- and cis-[OsF4Cl2]2- with Cl- the trans-isomers are formed stereospecifically. The pure fluoro-chloro-osmates(IV) are separated by ion exchange chromatography on diethylaminoethylcellulose. From the pairs of stereoisomers the cis-compounds are always first eluted, whereas the trans-complexes are moving faster in an electric field by 3 to 5% . The vibrational spectra of octahedral mixed ligand complexes are generally discussed according to point groups Oh, D4h, C4v, C3v and C2v. For the fluoro-chloroosmates(IV) all stretching and deformation bands are assigned. They are observed in the characteristic regions; ν(OsF): 625-490 > ν(OsCl): 360-300 > δ (FOsF): 275-210 > δ (FOsCl) > δ (ClOsCl): 190-150 > νL: < 100 cm -1.
ReNF4 · ReF5(NCl), ein Nitrido-Nitrenokomplex von Rhenium(VII)/ ReNF4 · ReF5(NCl), a Nitrido Nitrene Complex of Rhenium (VII)
Authors: Kafitz Willi , Dehnicke Kurt , Schweda Eberhard , Strähle Joachim
Published: February 2015

ReNF4 · ReF5(NCl) is prepared by direct fluorination of ReNCl4 with fluorine between 80 °C and 130 °C. The red crystals are extremely sensitive to moisture. The complex is characterized by the IR spectrum and by an X-ray structural investigation. ReNF4 · ReF5(NCl) crystallizes orthorhombically in the space group Pnma with 4 formula units per unit cell and with the cell dimensions a = 1440, b = 848, c = 776 pm (419 observed, independent reflexions, R = 13.9%). The complex consists of the molecules ReNF4 and ReF5(NCl), which are linked by a linear asymmetric fluorine bridge. The bridging fluorine atom is in trans-position to the nitrido ligand Re -F - 228 pm) and to the nitreno ligand (Re -F = 159 pm and Re= N - Cl 164 pm) correspond to triple 188 pm). The Re ≡ N bond lengths Re= N bonds.
Strukturverfeinerungen an den Cobalt(II)hexammin-Komplexen [Co(NH3)6](BF4)2 und [Co(NH3)6](PF6)2/ Structure Refinements of the Cobalt(II)hexammine Complexes [Co(NH3)6](BF4)2 and [Co(NH3)6](PF6)2
Authors: Kummer S. , Babel D.
Published: February 2015

Using single crystal X-ray data of the compounds [Co(NH3)6](BF4)2 (a = 1129.8(1) pm) and [Co(NH3)6](PF6)2 (a = 1195.9(1) pm) the anti-K2PtCl6 structure, space group Fm3m , was confirmed for both complexes (R ≈ 0.05). Fourier methods revealed essential disorder for the BF4
- anion only, the fluorine atoms of which remain concentrated, however, within the octants of the subcell opposite to the cobalt atoms. No indication of H bridging is found in the IR spectra. The Co-N bond lengths of 218.3(2) and 218.7(10) pm, resp.. in the cobalt(II)hexammine group are unusual long in both compounds.
31P-NMR-spektroskopische Untersuchungen an A4B3-Molekülen/ 31P NMR Spectroscopical Investigations of A4B3 Molecules
Authors: Blachnik R. , Wickelund U . , Schmitt P.
Published: February 2015

31P NMR data of sixteen molecules in the series P4SxSe3-x (x = 0 - 3), PyAs4-yS3, and PyAs4-ySe3 (y = 0 - 4), resp., are given. All molecules have a common structure, in which a basal ring of three V b-atom s is connected by three chalcogen atom bridges to an apical V b-atom . The dependence of the data on bond angles and electronegativities is discussed. A linear relationship was found betw een chemical shift and an angle increment I=11.3 (∢ endo - 60°) + 5.5 (∢ exo -103°), which describes the bond angle deviations from the reference molecule P4S3.
Transition Metal Allyls, V. The Preparation and Structure of [NiX(PmenthylR1R2)(η3-allyl)] Complexes
Authors: Brandes H. , Goddard R. , Jolly P. W. , Krüger C. , Mynott R. , Wilke G.
Published: February 2015

A number of adducts formed by reacting [NiX(η3-allyl)]2 complexes with optically active tert.- phosphines, in which optically active centres are found both at the phosphorus atom and in a substituent, have been isolated and their structures investigated in solution by NMR spectroscopy. The absolute configuration of the phosphine in [NiCl{Pm enthyl(Me)But}(η3-C3H5)] has been determ ined by X-ray crystallography. The relevance of the results to the nickel-catalyzed asymmetric codimerisation of alkenes is discussed.
Synthese und Kristallstruktur von TlI3(3-CH3C5H4NO)2, einem Komplex des dreiwertigen Thalliums / Synthesis and Crystal Structure of TlI3(3-CH3C5H4NO)2, a Complex of Trivalent Thallium
Authors: Bermejo M. R. , Castineiras A. , Gayoso M. , Hiller W. , Englert U. , Strähle J.
Published: February 2015

TlI3(CH3C5H4NO)2 is obtained in acetonitrile by the reaction of TlI with iodine and 3-methyl- pyridine-N-oxide. It crystallizes monoclinic in the centrosymmetric space group C2/c with lattice parameters at 190 K, a = 1756.5(8), b = 780.7(5), c = 1397.1(4) pm, β = 110.26(3)° and Z = 4. The structure consists of monomeric complexes, in which the Tl atom shows a fivefold coordina­tion in form of a slightly distorted trigonal bipyramid, the I atoms being located in the equatorial plane. The symmetry of the complex is C2 whereby the Tl atom and one of the I atoms occupy the twofold axis.
Phase Changes in Fe(III)OCl–RNH2-Intercalation Complexes
Authors: Weiss Armin , Choy Jin Ho
Published: February 2015

Iron(III)oxide chloride is capable of intercalating ammonia and amines into its layer lattice. Long chain molecules form bilayers with extended chains almost perpendicular to the host lattice layers at room temperature (intercalate composition): FeOCl · (0.54 ±0.03)n -CxH2x+1NH2 with x ≥ 12) and tilted by 57° at about 100-110 °C (intercalate composition: FeOCl · (0.45 ±0.02)n-CxH2x+1NH2 with ≥12). The temperature-dependent changes in basal spacings between 20 and 110 °C are complex. Above 120 °C the layers of the host lattice are altered irreversibly by substitution and HCl-release to FeOCl1-y(-NHCxH2x+1)y with y ≤ ca. 0.4.
The He(I) and He(II) Photoelectron Spectra of Tm2Zn (Tm = (C5H5)Fe(CO)2, (C5H5)M(CO)3; M = Cr, Mo, W)
Authors: Louwen Jaap N. , Stufkens Derk J. , Oskam Ad
Published: February 2015

UV photoelectron spectra of the title compounds are reported. Assignments are made with the help of He(I)/He(II) intensity differences, shift effects upon substitution and comparison with related molecules. Previously drawn conclusions about the electronic structure of similar com­plexes also hold for the compounds. It is indicated that the ionization energy for the symmetric metal-metal bond strongly depends on the overlap between transition and post-transition metals.
Dimethyl (alkylthio)- und Dimethyl(arylthio)gallane – Darstellung und Eigenschaften / Dimethyl(alkylthio)- and Dimethyl(arylthio)gallanes – Synthesis and Properties
Authors: Hoffmann Gerhard G.
Published: February 2015

The nucleophilic substitution reactions between dimethylgalliumchloride (1) and the silyl sul­fides (CH3)3SiSR (R = CH3, C2H5, n-C3H7, i-C3H7, Ph and CH2Ph) (2-7) in benzene result in the formation of the moisture-sensitive dimethyl(alkylthio)- and dimethyl(phenylthio)gallanes (CH3)2GaSR (R = CH3, C2H7, n-C3H7, i-C3H7, Ph and CH2Ph) (8-13). Compounds 8-11 are trimeric in benzene solutions, whereas compounds 12 and 13 appear to be monomeric. The synthesis of dimethylgalliumchloride starting from trimethylgallane or methylgalliumdichloride and galliumtrichloride is reported as well.
Tetrachloroantimon-trimethylsilylcarbodiimid-Schwingungsspektrum und Kristallstruktur / Tetrachloroantimony Trimethylsilylcarbodiimide Vibrational Spectra and Crystal Structure
Authors: Rajca G. , Schwarz W. , Weidlein J.
Published: February 2015

Tetrachloroantimony trimethylsilylcarbodiimide, Cl4SbNCNSiMe3, has been synthesized by the reaction of SbCl5 with Me3SiNCNSiMe3 in a 1:1 molar ratio. The pale yellow compound is dimeric in solution and in the solid state and has according to the vibrational spectra a centrosymmetric structure of C2h symmetry. The X-ray structure determination shows the monoclinic space group P21/c with two dimeric units per cell. The structure was refined to an R-value of 0,04.
Neuartige basische Liganden für die homogenkatalvtische Homologisierung von Methanol zu Ethanol, III [1]. Der Einfluß neuartiger P–N-Liganden auf die Selektivität und den Umsatz bei der Ethanolsynthese aus Methanol / Novel Basic Ligands for the Homogeneous Catalytic Homologation of Methanol to Ethanol, III [1]. The Impact of Novel P-N-Ligands on the Selectivity and Conversion for the Synthesis of Ethanol from Methanol
Authors: Lindner Ekkehard , Rauleder Hartwig , Wegner Peter
Published: February 2015

The N -P-N-ligands RP(XC5H4N)2 (1b′, c′, b″, c″) [X = O: R = t-Bu (b′), Me (c′); X = NH: R = t-Bu (b″), Me (c″)] are characterized by their different complex chemical behaviour towards group VI metal carbonyl derivatives. By reaction of 1b′, c′, b″, c″ with (CH3CN)3M(CO)3 the complexes (OC)3M[RP(XC5H4N)2] (2b′, c′, 3b″) and (OC)4W|[CH3P(NHC5H4N)2] (3c″) [M = Mo (2).,W(3)] are formed in which the ligands are tridentate and bidentate, respectively. This difference can be explained with the existence of hydrogen bridge linkages between NH and pyridyl groups in 3c″. Homologation experiments of methanol with 1, CoOAc: and I2 as an activator show high conversions (85%) with about 40% of ethanol selectivity. The lowest selectivities are found with 1c″.
Darstellung und Struktur von Bromoarsenaten(III) organischer Stickstoffbasen / Preparation and Structures of Bromoarsenates(III) of Organic Nitrogen Bases
Authors: Kaub J. , Sheldrick W. S.
Published: February 2015

N-methylanilinium-tetrabromoarsenate(III) (1). pyridinium-tetrabromoarsenate(III) (2), and tris-pyridinium-nonabromo-diarsenate(III) (3) habe been prepared and their structures deter­mined by X-ray structural analysis. 1 contains discrete As2Br8
2- anions with Ci symmetry, 2 infinite (AsBr4
-)n chains and 3 discrete As2Br9
3- anions. Pseudo-octahedral coordination is ob­served for the As atoms in 1. The bridging As-Br bonds in As2Br9
3- are markedly stronger than the analogous As-Cl bonds in the tris-pyridinium salt of As2Cl9
3-.
β-HydroxyethyIperoxyl Radicals: A Study of the γ-Radiolysis and Pulse Radiolysis of Ethylene in Oxygenated Aqueous Solutions
Authors: Piesiak Alicja , Schuchmann Man Nien , Zegota Henryk , Sonntag Clemens von
Published: February 2015

Hydroxyl radicals (and H atoms) generated in the radiolysis of N2O-containing water add to ethylene forming β-hydroxyethyl radicals (and ethyl radicals). In the presence of oxygen these are converted into the corresponding peroxyl radicals which decay bimolecularly (2k = 2 x 108 M-1s-1) as measured by pulse radiolysis. The major products (G values in brackets) are glycolaldehyde (3.3). formaldehyde (1.6), ethylene glycol (0.8), acetaldehyde (0.5). organic peroxidic material (0.5). and hydrogen peroxide (2.4) (dose rate 0.26 Gy s-1, pH 5.6). A material balance has been obtained with respect to the primary water radicals (6.0) and oxygen uptake (4.8). The products and their yields can be accounted for if in the rate determining step atetroxide is formed which decomposes via three major pathways leading to: (i) H2O2 and two molecules of glycolaldehyde (ca. 45%), (ii) O2, glycolaldehyde and ethylene glycol (ca. 30%). and (iii) O2. two molecules of formaldehyde and two CH2OH radicals (ca. 15%). A 1,2-H shift of intermediate oxyl radicals is unimportant in this system.
Übergangsmetallkomplexe mit Schwefelliganden, IX. Templat-Synthese und Reaktionen der Eisen(II)-Komplexe [Fe(CO)2(C6H4S2–X–S2C6H4)] mit kurz- und langkettig verbrückten o-Benzoldithiolat-Liganden, X = (CH2)n, n = 1,3–8,12; X = CH2COCH2; Synthese der freien Liganden / Transition Metal Complexes with Sulfur Ligands, IX* Template Synthesis and Reactions of the Iron(II) Complexes [Fe(CO)2(C6H4S2–X–S2C6H4)] with o-Benzenedithiolate Ligands. Bridged by Short as well as Long Chains (X = (CH2)n, n = 1,3–8,12; X = CH2COCH2); Synthesis of the Free Ligands
Authors: Sellmann Dieter , Reißer Wolfgang
Published: February 2015

Alkylation of [Fe(CO)2(S2C6H4)2]2- by Br(CH2)nBr (n = 1,3-6) or CICH2COCH2Cl yields [Fe(CO)2(C6H4S2-(CH2)n-S2C6H4)] and [Fe(CO)2(C6H4S2-CH2COCH2-S2C6H4)]. respectively. With long-chain dibromoalkanes (n = 7,8,12) the oligonuclear complexes [Fe(CO)2(C6H4S2 - (CH2)n - S2C6H4)]x also form; in these cases the mononuclear complexes can be obtained by dilution methods. Growing length of the bridge between the thioether donor atoms favours the loss of CO and formation of [Fe(CO)(C6H4S2-(CH2)3-S2C6Η4)]2 and [Fe(C6H4S2 - (CH2)n-S2C6H4)]x (n = 1,4-8,12). respectively; substitution rate of CO by PMe3 is increased as well. Hydrolysis of the Fe(CO)2 complexes by HCl gives the free tetradentate thioetherthiol ligands HSC6H4S - (CH2)n - S2C6H4SH.
Notizen: The Isolation and Structure of Lahoricine, a New Indolenine Alkaloid from Ervatamia coronaria
Authors: Atta-ur-Rahman  , Daulatabadi Nader , Muzaffar Anjum
Published: February 2015

A new indolenine alkaloid, “Lahoricine” has been isolated from the leaves of Ervatamia coronaria to which structure 1 has been assigned.
Polymere Methylphosphono-vanadate: Struktur von K[CH3PVO5]·H2O / Polymeric M ethylphosphono Vanadates: Structure of K[CH3PVO5]·H2O
Authors: Mattes Rainer , Preuß Annegret , Richter Kurt-Ludwig
Published: February 2015

Polymeric phosphono-vanadates MI[CH3PVO5]·H2O (M=K, NH4) and the acid H[CH3PVO5]·H2O have been prepared. K[CH3PVO5]·H2O crystallizes in the trigonal space group P3121 with a = 1111.2(2) and c = 1004.0(3) pm, and consists of an open structure of corner sharing V-O- and CH3-P-O-polyhedra. Polyhedral chains form helices along the screw axis of the space group. The vanadium polyhedron can be described as highly distorted trigonal bipyramid with two terminal oxygen atoms.
Synthese und Reaktivität von [5-exo-Phosphino-η4-cyclopentadien]- tricarbonyleisenkomplexen / Synthesis and Reactivity of [5-exo-Phosphino-η4-cyclopentadiene] Tricarbonyliron Complexes
Authors: Weber Lothar , Reizig Klaus
Published: February 2015

The novel 5-exo-phosphino-η4-cyclopentadienyl complexes (η4-C5H5PR1R2)Fe(CO)3 (4) (a: R1=R2=SiMe3; b:R1=t-Bu; R2=SiMe3) are obtained by the nucleophilic addition of LiPR1R2 to the carbocyclic ligand in [(η5-C5H5)Fe(CO)3]PF6. At room temperature 4a, b are converted into (η5-C5H5)(CO)2Fe-PR1R2 (5a, b).
Difluor-bis(methylamino)-t-butyl-phosphoran Darstellung und NMR-Daten / Difluoro-bis(methylamino)-t-butyl-phosphorane Preparation and NMR Data
Authors: Heckmann Gernot , Fluck Ekkehard , Svara Jürgen
Published: February 2015

Preparation and properties of the title compound are described. It is present as a mixture of the isomers I and II. The 1H, 13C, 19F, and 31P NMR spectra are discussed in detail. For amino fluoro phosphoranes rules for the estimation of NMR chemical shifts and coupling constants are given.
Structural Studies of Benzene Derivatives, XII [1]. The Molecular Structure of 3,5-Dimethylbenzoic Acid in the Crystal, and a Comparison with the Gas Phase Structure of Related Molecules
Authors: Colapietro Marcello , Domenicano Aldo , Marciante Clara , Portalone Gustavo
Published: February 2015

The molecular structure of 3,5-dimethylbenzoic acid has been accurately determ ined by X-ray crystallography. The crystals are monoclinic, space group P21/n, with a = 8.165(2), b = 6.992(1), c = 14.422(2) Å , β = 93.21(2)°, Z = 4. The structure has been refined by full-matrix least-squares techniques to R = 0.0415 on 1662 counter intensities. The carbon skeleton of the benzene ring has C2v symmetry within experimental error. The six aromatic C-C bond distances do not differ significantly from each other; some of the internal ring angles, however, deviate from 120° by as much as 2°. After correction for systematic effects, such as the asphericities of the electron density distribution and the libration of the molecule in the crystal, the mean aromatic C-C bond distance is 1.401(1) Å , and the two independent C-CH3 bond distances are 1.509 and 1.511(3) Å. These values are in outstanding agreement with the corresponding rg distances measured by gas electron diffraction in p-xylene (1.400±0.003 Å and 1.512±0.003 Å , respectively) and mesitylene (1.401 ±0.002 A and 1.509±0.002 Å, respectively). The deviations of the ring angles from 120° are interpreted fairly well as arising from the superposition of separate, independent angular distortions from each substituent.
Zur Reaktion von 1-Sila-2,4-cyclohexadien mit tert-Butyllithium/Trimethylchlorsilan / On the Reaction of 1-Sila-2,4-cyclohexadiene with tert-Butyllithium/Trimethylchlorosilane
Authors: Jutzi Peter , Berg Gabriele , Otto Cornelius , Wippermann Thomas
Published: February 2015

In the system 1-sila-2,4-cyclohexadiene (l)/tert-butyllithium/trimethylchlorosilane the following reaction types have been observed: nucleophilic substitution, metallation, addition of tert-butyllithium to the diene fragment, addition of lithium hydride to the diene fragment, silicon-carbon bond cleavage, and transmetallation. The resulting products 2-11 have been characterised by their 1H and 13C NMR data; the compounds 2, 3, 6, 8 and 10 could be isolated in a pure form. The relative quantities obtained of the compounds 2-11 depend on the reaction conditions (solvent, temperature, order of addition).
1H and 13C NMR Spectroscopic Studies of the Complexation of Phenylenedioxydiacetamides with Calcium and Potassium Cations in Solution
Authors: Lin Whei Oh , Souza Maria C. B. V. de , Alt Helmut G.
Published: February 2015

Phenylenedioxydiacetamides are examples of noncyclic ionophors that are able to form 2:1 complexes with the cations Ca2+ and K+ in acetone, methylene chloride or acetonitrile solution. The chelation abilities and coordination modes of 12 derivatives were investigated systematically by IR, 1H NMR and 13C NMR spectroscopy. The results indicate that only the 1,2-phenylenedioxydiacetam ides function as ligands; while the 1,3-derivatives do not coordinate. The ionophors 1-8 act as tetradentate chelating ligands with all four oxygen atoms involved in bonding to the cation. Irrespective of its charge, each cation is coordinated by two ionophors.
1.3-Dichlor-5-trifluormethyl-1,3-dithia-2,4,6-triazin / 1.3-Dichloro-5-trifluoromethyl-1,3-dithia-2,4,6-triazine
Authors: Höfs Hans-Ulrich , Hartmann Gabriele , Mews Rüdiger , Sheldrick George M.
Published: February 2015

The preparation of cyclo-(CF3CN)(NSCl)2 (2) from CF3CN and (NSCl)3 is reported. Dechlorination of 2 by Zn in liquid SO2 is found to yield either CF3CN3S2 or mainly CF3CN2S2, depending on the reaction conditions. The structure of 2 was determined from single crystal data.
The Chlorination of Di-tert-butyl-2-naphthol+
Authors: Streich Edgar , Rieker Anton
Published: February 2015

Chlorination of the di-tert-butylation product of 2-naphthol leads to 3,6-di-tert-butyl-1,1-dichloro- l,2-dihydronaphthalen-2-one (4a) instead of 1,6-di-tert-butyl-1,3-dichloro-1,2-dihydronaphthalen-2-one (2) as reported [2], The structural proof was mainly offered by 13C NMR spectroscopy. The influence of annelation and chlorine substitution in 1,2-dihydronaphthalen-2-ones on δ13c=o is discussed, which is of importance for the use of δ13c=o for a general discrimination between ortho- and para-quinolide structures.
On the Involvement of Singlet Oxygen in the Biosynthesis of Oxygenation Products of the Furocoumarin Imperatorine
Authors: Mol Nicolaas J. de , Reisch Johannes , Henegouwen Gerardus M. J. Beijersbergen van
Published: February 2015

The role of singlet oxygen (1O2) in the photo-oxidation of the furocoumarin im peratorine was investigated in vitro. Irradiation with visible light and sensitization with methylene blue yielded the imperatorine oxidation product isogosferol and the corresponding ketone as main products. The involvement of 1O2 was dem onstrated by studying the rate of oxidation under conditions that affect the lifetime of 1O2. Com pared to a range of other furocoumarins, im peratorine appeared to be moderately active as a 1O2 generator. The extent of 1O2 production correlated with the skin sensitizing activity. Upon irradiation of im peratorine itself with UVA light (360 nm) no isogosferol formation is observed, probably as a consequence of its photochemical instability. Irradiation with visible light (λ > 400 nm) of a chlorophyll chromophore containing sensitizer in the presence of imperatorine, yielded isogosferol and the corresponding ketone product. This dem onstrates that in the formation of 1O2 oxidation products of imperatorine in plants naturally occuring sensitizers e.g. chlorophyll and visible light are involved, rather than 1O2 produced by im peratorine or other furocoumarins and UVA light. The protective effect on the chlorophyll sensitized im peratorine oxidation by the 1O2- and chlorophyll triplet quencher β-carotene was demonstrated in a lipophilic solvent.
Synthese und Kristallstruktur von Tris(2,2'-bipyridin)eisen(II) μOxo-bis(trichloroeisen(III)), ein Salz mit dem Anion Fe2OCl6
2-
Authors: Weiss Herbert , Strähle Joachim
Published: February 2015

[Fe(2,2'-bpy)3][Fe2OCl6] is obtained in form of red, air stable crystals by oxidation of Fe(bpy)Cl2 with O2 in acetonitrile. It crystallizes in the monoclinic space group P21/c with Z = 4. The crystal structure contains Fe(bpy)3
2+ and Fe2OCl6
2- ions. The anion exhibits a bent oxobridge with Fe-O-Fe = 148,1° and Fe-O distances of equal length (176,5 pm). In the IR spectrum νas Fe-O-Fe is observed at 850 cm-1, the Fe-Cl valence vibrations at 362 and 317 cm -1.
Darstellung, 11B-NMR- und Schwingungsspektren der oktaedrischen closo-Boratanionen B6X6
2-; X = H, Cl, Br, I
Authors: Preetz W. , Fritze J.
Published: February 2015

On treatment of Na2B6H6 with halogens in aqueous alkaline solution, the hexahalogenoborates B6X6
2-, X = Cl, Br, I, are formed. Their octahedral structure is proved by 11B NMR spectroscopy. The chemical shifts in relation to BF3 · OEt2 increase within the series H (-13.5) < Cl (-17.4) < Br (-18.5) < I (- 27.5 ppm ). The IR and Raman spectra are assigned according to point group Oh. The internal vibrations of the B6-cage, observed in the range 750-1250 cm-1 at nearly unchanged positions, are distinguishable from vibrations mainly originating from motions of the X6-shell against the rigid B6-cluster.
Phthalocyanine von Cobalt(III): Darstellung, Resonanz-Raman-, Infrarot- und elektronische Absorptionsspektren von [CoX2Pc(1—)] (X = Cl, Br) and [CoX2Pc(2-)]- (X = OH, F, CI, Br)
Authors: Homborg H. , Kalz W.
Published: February 2015

The preparation of anionic phthalocyaninato-cobaltates(III) [CoX2Pc(2-)]- (X = OH . F, CI, Br) is described. The UV -VIS. IR and Resonance-R am an (RR ) spectra are measured and com pared with those of the complexes [CoX2Pc(1 -)] (X = Cl, Br) containing the phthalocyanine-π-cation- radical.The characteristic spectroscopical differences for the Pc(1-)- and Pc(2-)-Ligands are discussed. Besides the typical B-, Q- and N-transitions of the Pc(1 -)- and Pc(2 -)-ligand additional weak bands are observed in the UV -VIS spectra for both dichloro- and dibromocomplexes. These bands are assigned to X (π , σ) → Co electron transfer a2u(πx), a2u(σx) → a1g(d); for the Pc(1 - )-complexes Cl(π) is at 22.9, Cl(σ) at 38.9. Br(π-) at 19.6 and Br(σ) at 36.4 kK. For the Pc(2-)-complexes these bands are slightly red-shifted by about 0.5 kK. The assignment is confirm ed by the RR-spectra. For both dichloro- and dibromo-complexes the sym. (Co-X)- stretching vibration (a1g, ν1) is strongly RR-enhanced and up to four overtones of ν1 are observed (for Pc(2-): ν ( Co - X ) for X = Cl: 270. Br: 165 cm-1; for Pc ( 1 - ) : X = Cl: 280. Br: 168 cm-1). The antisym. (Co -X)-stretching vibration (a2u) is observed in the FIR spectra (for Pc(2 -): ν(Co-X) for X = F: 546. Cl: 333. Br: 243 cm-1; for Pc ( 1 - ) : X = Cl: 326. Br: 250 cm-1).
Iridiumkomplexe des Vaska-Typs mit Triisopropylphosphan-Liganden [1]
Authors: Werner H. , Höhn A.
Published: February 2015

The complexes trans-[IrClL(PiPr3)2] (L = CO , py, CH3CN) were prepared from [(C8H14)2lrCl]2 via[IrCl(PiPr3)2] as intermediate. rrans-[IrCl(CO)(PiPr3)2] reacts with LiC2Ph to form trans- [IrC2Ph(CO)(PiPr3)2] which on treatment with HX produces [IrH X(C2Ph)(CO)(PiPr3)2] (X = Cl, CF3CO2). The trifluoroacetate ligand is displaced by iodide to give [IrHI(C2Ph)(CO)(PiPr3)2]. trans-[IrCl(N2)(PiPr3)2] is obtained from the carbonyl complex and 2-furfurylazide.
Darstellung und Eigenschaften der tert-Butyliminovanadium(V)-Verbindungen tC4H9N =VX3 (X = Br, OR)
Authors: Preuss Fritz , Towae Willi , Kruppa Volker , Fuchslocher Edith
Published: February 2015

tC4H9N = VBr3 has been prepared by reaction of the trichloride with hydrogen bromide dissolved in benzene. The structure of the 2.2'-dipyridyl complex [tC4H9N = VBr3 · C10H8N2] has been found to be octahedral with meridional arrangement of bromide. Syntheses of iC3H7N = V(OR)3 and iC3H7N = V(OR)3 are described. The properties of these compounds are studied by chemical reactions such as redistribution, transamination and alcoholysis. The 51V NM R spectra of the alkyliminovanadium(V) compounds are discussed; the constants of 51V , 14N coupling have been determined. The oxovanadium (V) complex [VO (OCH3)3-V O(OCH3)2Cl] has been prepared; all attempts to prepare VO(OCH3)2Cl have not been successful.
Funktionelle Trimethylphosphanderivate, XXII [1] Struktur und Reaktivität von Lithium-tris(dimethylphosphino)methanid sowie Molekülstruktur von / Functional Trimethylphosphine Derivatives, X X II [1]
Structure and Reactivity of Lithium-tris(dimethylphosphino)methanide
and Molecular Structure of
Authors: Karsc Hans Heinz , Weber Lothar , Wewers Dietmar , Boese Roland , Müller Gerhard
Published: February 2015

The reaction of Lithium-tris(dimethylphosphino)methanide with methyl iodide is sensitive to the choice of the solvent and reaction conditions; in pentane at room temperature and in the presence of tetramethylethylenediamine, Me3P = C(PMe2)2 is the major product, whereas in tetrahydrofuran, (Me2P)3C -CH3 is formed predominantly. Under similar conditions, Lithium-bis- (dimethylphosphino)methanide reacts with Mel to give (Me2P)2C(CH3)H as the main product. An X-ray structure determination of the tetrahydrofuran solvate of LiC(PMe2)3 reveals this compound to be dimeric with one solvent molecule coordinating to Li. A pseudo tetrahedral coordination sphere around each Li atom is completed by two phosphino groups of one [C(PMe2)3]- anion and a contact ion pair interaction with the carbanionoid center of the second. The crystals are monoclinic, space group P21/n, with a = 928.5(2), b = 1250.8(3), c = 1407.9(3) pm, β = 100.07(1)°, V = 1609.9 • 106 pm3 Dc = 1.13 g/cm3 for Z - 4 at -40 °C. Full-matrix least-squares refinement of 249 parameters based on 2158 reflections converged at R = 0.029. The ligand properties of (Me2P)3CCH3 are tested in its reactions with (CO)4Cr(C7H8) and (CO)5Cr[CH2S(O)Me2] from which

and

may be isolated. The latter crystallizes in the monoclinic space group P21/c with a - 1218.5(3). b = 881.7(3), c = 1824.1(4) pm, β = 106.66(2)°, V = 1877.6(9) • 106 pm3, Dc = 1.37 g/cm3 for Z = 4. Least-squares refinement of 218 parameters on 1615 reflections produced R = 0.063. The structure determination confirms the molecule to contain a five-membered

heterocycle in an approximate envelope conformation.
Ligand Exchange in FAB Mass Spectrometry of Monomerie and Dimeric Corrinoids
Authors: Grotjahn Lutz , Ernst Ludger
Published: February 2015

In the Fast Atom Bombardment (FAB) mass spectra of monomeric and dimeric corrinoids, exchange of metal-bound ligands against matrix particles is observed which leads to pseudo molecular ions. Negative ion FAB mass spectra in particular, give distinct information on the intact molecular units.