bluuebunny/crossref_metadata_2025 huggingface dataset:
Beiträge zur Chemie des Phosphors, 116 Kernresonanzspektren und Kristallstruktur von Tri-tert-butylcyclotriphosphan / Contributions to the Chemistry of Phosphorus, 116 NMR Spectra and Crystal Structure of Tri-tert-butylcyclotriphosphane
Authors: Hahn Josef , Baudler Marianne , Krüger Carl , Tsay Yi-Hung
Published: February 2015

A complete analysis of the 31P, 13C and 1H NMR spectra of tri-tert-butyl-cyclotriphosphane (1) was carried out and the resulting NMR parameters were correlated with the X-ray data of the molecule. It was found, that increasing P-P-C-bond angles correspond to a downfield shift and an increase of the absolute values of the negative 1J(PP) and 1J(PC) coupling constants. Generally, the chemical shifts of cyclotriphosphanes as well as of larger cyclic phosphanes depend on the endo- and exocyclic bond angles, the dihedral angle between the electron lone pairs of adjacent P-atoms, and the β-effect. On the basis of the X-ray and chemical shift data of 1, the bond angles of other cyclotriphosphanes can be deduced from their δ(31P) values.

1 crystallizes triclinically in the space group P1̄ with Z = 4 formula units. The X-ray analysis confirms the NMR-spectroscopically determined three-membered ring structure with the tert-butyl substituents on either side of the ring plane. Due to steric hindrance between the two tert-butyl groups in cis position, the corresponding P-P-C-bond angles show the largest values so far observed for organylcyclophosphanes.
Some New Conducting Solids: Cation-Deficient Metal Dimercaptodithiolenes and Selenium Analogs
Authors: Papavassiliou G. C.
Published: February 2015

Some new conducting solids of the general formula ZxM(C3S5)2 and its selenium analogs (where: Z = Bu4N, Na, Li, NH4; M = Ni, Pd, Pt etc.; 0 < x ≤ 1) were prepared and studied.
S4N4 und seine Derivate: Darstellung, Struktur und Thermolyse von CuBr · S4N4 / S4N4 and its Derivatives: Preparation, Structure and Thermolysis of CuBr · S4N4
Authors: Thewalt Ulf , Müller Bernhard
Published: February 2015

The crystalline black polymeric CuI complex CuBr · S4N4 can be prepared in high yield from Cu(NO3)2 · 3 H2O, NH4Br and S4N4 in methanol. An X-ray structure analysis shows that it is isostructural with CuCl · S4N4. The crystals contain [CuBr]∞ chains and the Cu atoms of adjacent chains are bridged by S4N4 groups. The Cu atoms have an almost tetrahedral coordination. The 1,3-N,N′-bonded S4N4 group has the same conformation and, within narrow limits, the same dimensions as free S4N4. Thermolysis of CuBr · S4N4 at 180 °C yields among other products CuBr, S4N4, and S2N2.
Röntgenograpliische und magnetische Untersuchungen an perowskitverwandten Cyanoverbindungen CsMIIMIII(CN)6 / X-Ray and Magnetic Studies of Perovskite-Related Cyano Compounds CsMIIMIII (CN)6
Authors: Griebler W.-D. , Babel D.
Published: February 2015

The perovskite-related cyano compounds CsMIICr(CN)6 (MII = Mn, Zn), CsZnFe(CN)6 and CsMnCo(CN)6 (Mn = Mn-Cu) are characterized by their IR active C - N and MIII-CN stretching frequencies, their lattice constants and their magnetic susceptibilities (4,2-295 K). Except for CsCuCo(CN)6, which is tetragonally distorted, all compounds crystallize cubically face-centered (with lattice constants in the range from 1020 to 1084 pm). The magnetic behaviour indicates low spin MIII and high spin MII states, supporting the IR evidence for a strictly ordered MIII-CN-MII arrangement. The compound CsMnCr(CN)6 is ferrimagnetic, with a Néel temperature of TN = 90 K and an extrapolated spontaneous magnetization of a = 2,30 μB at 0 K. Superexchange interactions via the cyano bridges are considered responsible for the ferrimagnetism observed.
Meso-rac-Ph(X)P-(CH2)4-P(X)Ph-Liganden in Komplexen des Typs (CO)4M cis(L-L), Untersuchung der Stereoisomerie durch 31 P{ 1 H}-und 13C{1 H}-NMR-Spektroskopie / Meso, rac-Ph(X)P-(CH2)4-P(X)Ph Ligands in Complexes of the Type (CO)4M cis(L-L), Investigation of Stereoisomerism by 31P{1 H} and 13 C{ 1 H} NMR Spectroscopy
Authors: Diemert Klaus , Kuchen Wilhelm , Kutter Jürgen
Published: February 2015

By reaction of M(CO)6 (M = Cr, Mo, W) with the bifunctional aminophosphane Ph(NEt2)P-(CH2)4-P(NEt2)Ph (L-L) octahedral complexes (CO)4M cis(L-L) are obtained. While it is shown by 31P{1H} NMR spectroscopy, that these complexes contain meso-and rac-(L-L) to a different extent, there is evidence from 13C{1H} NMR data obtained for the Mo complex, that the rac-ligand always prevails. As racemisation is observed when the Mo complex reacts with HBr to give (CO)4Mo-cis[Ph(Br)P-(CH2)4-P(Br)Ph] an SN
1-mechanism is suggested for this reaction.
Synthesis and Structure of 1,2-Bis(2,4,6-tri-fert-butylphenyl)ethane
Authors: Winter Werner , Butters Thomas , Rieker Anton , Butsugan Yasuo
Published: February 2015

The title compound 9, C38H62, was prepared by dehalogenation of 2,4,6-tri-tert-butyl-benzyl chloride (7a). It crystallizes in the monoclinic space group C2/c with Z = 4. a = 10.923(7), b = 17.910(3), c = 17.395(3) Å and β = 91.87(3)° (the cell constants refer to 173 K). The structure was solved by direct methods and refined by full-matrix least squares to R = 0.073 for all 3853 reflexions (|F0| > 0). On account of steric repulsions, the central ethane bond, which lies on a twofold crystallographic axis, is stretched to 1.567(4) Å. Close packing of the molecules in layers parallel the ac-plane leads to boat-deformations of the benzene rings. Room-temperature data sets of weakly diffracting crystals [a = 10.948(6), b= 17.97(1), c= 17.52(2) and β = 91.9(1)°] do not give rise to an artificial shortening of the central ethane bond of 9. Evidently, poor data quality or lack of resolution have not to be considered as an explanation for the unusual short ethane bond [1.47(3) Å] in the first undamped hexaphenylethane [Stein, Winter, and Rieker (1978)].
Synthesis of N-Trityl-L-homoserine
Authors: Barlos Kleomenis , Theodoropoulos Dimitrios
Published: February 2015

L-Homoserine was tritylated via its silylated product with Me2SiCl2 or Ph2SiCl2 in 65-68% yield. Also N-Trt-L-methionine upon treatment with Mel and degradation of the resulting sulfonium salt with KOH yielded N-Trt-L-homoserine in 75% yield. Both routes provided N-Trityl-L-homoserine with identical physical data. In contrast to N-alkyloxycarbonyl-L-homoserine derivatives, N-Trt-L-homoserine shows no tendency to spontaneous lactonization.
0-(Triphenylstannyl)-N-acyl-N-arylhydroxylamines
Authors: Das Mrinal K. , Nath Matilal
Published: February 2015

A number of O-(triphenylstannyl)-N-acyl-N-arylhydroxylamines have been synthesized. Results of IR, electronic (UV) and 1H NMR spectroscopic measurements suggest that these compounds possess trigonal bipyramidal configuration around a pentacoordinated tin atom with phenyl groups cis to each other.
Keto-Steroids, I Conversion of Diosgenin to 6 β-Methylpregn-4-ene-6 α,20-diol-3,16-dione
Authors: Dawidar A. M. , Saleh A. A. , Abdel-Galil F. M. , Abdel-Malek M. M.
Published: February 2015

The reaction of diosgenin (1) with hydrogen peroxide/formic acid was investigated. As a result of this work, 5 α (25 R)-spirostane-3 β,5,6 β-triol (2) was prepared in 79% yield and 5 α-pregnane-3 β,5,6 β,16 β,20 α-pentol (3) in 80% yield. The pentol (3) was oxidised to 5 α-pregnane-3 β,5,10 β,20 α-tetrol-6-one (5) without forming its 16 β,20 α-isopropylidenedioxy derivative (4). Reaction of product 5 with CH3Mgl to give 6-methylpregnane derivative was unsuccessful. Therefore, product 7 was oxidatively degraded by H2O2/HCOOH to the 10-keto pregnane derivative (13) and its structure was proved through its transformation to 6 β-methylpregn-4-ene-6 α,20 α-diol-3,16-dione (15).
Synthese von 1.2.4-Oxadiazolyl-und 1.2.4-Thiadiazolylvinylphosphaten und deren biologische Wirkung / Synthesis of 1,2,4-Oxadiazolyl-and 1,2,4-Thiadiazolylvinylphosphates and their Biological Activity
Authors: Kübel Börries , Knauf Werner , Waltersdorfer Anna
Published: February 2015

2-(1,2,4-Oxadiazol-5-yl)vinylphosphates and 2-(1,2,4-thiadiazol-5-yl) vinylphosphates are prepared from the corresponding chlorophosphates and 5-acetonyl-1,2,4-oxadiazoles and 5-acetonyl-1,2,4-thiadiazoles resp. Some of the oxazolylvinylphosphates are effective insecticides and acaricides, but the corresponding thiadiazole derivatives have almost no effect.
Triazolyloximinoderivate, ihre Synthese und biologische Wirkung / Triazolyloximino Derivatives, their Preparation and Biological Activity
Authors: Kocur Jean , Mildenberger Hilmar , Sachse Burkhard
Published: February 2015

Triazolyloximinoethers are fungicides with high activity. Methods for the synthesis of these compounds and their stereochemistry are reviewed.
Chinazolinderivate, ihre Herstellung und biologische Wirkung / Quinazolines, their Preparation and Biological Activity
Authors: Schönowsky Hubert , Sachse Burkhardt
Published: February 2015

Quinazolines are fungicides with high activity. Methods to synthesis these compounds are reviewed.
Neue Benzylester von Cyclopropancarbon- und Phenylessigsäuren als potentielle Insektizide / New Benzylic Esters of Cyclopropanecarboxylic and Phenylacetic Acids as Potential Insecticides
Authors: Welter Wolfgang , Hüttelmaier Thomas , Matterstock Karl , Mildenberger Hilmar
Published: February 2015

Pyrethroids are known insecticides with a great potency to a wide range of insect species. Derivatizations at the benzylic position and at the second aromatic ring system of these pyrethroids yielded new benzylic esters with insecticidal activity. Methods for the synthesis of these compounds are reviewed.
Notizen: 2,4′ -Oxybispyridine
Authors: Rockley Jean E. , Summers Lindsay A.
Published: February 2015

2,4′-Oxybispyridine is synthesised by reacting 4-nitropyridine with the silver salt of 2-hydroxy-pyridine.
The Defensive Secretion of Aspavia brunna (Schout) (Hetetoptera: Pentatomidae)
Authors: Akpata M. I. , Olagbemiro T. .
Published: February 2015

The pungent odours emitted by true bugs when disturbed have captured the attention of numerous students of the Heteroptera. Studies of the chemical composition of the secretion of these stink bugs have shown the presence of alkanes, alkenyl acetates, alcohols and unsaturated aldehydes [1-3]. Most of these chemicals are employed as chemical warfare against the onslaught of microbial, vertebrate and in-vertebrate attackers [4], We herein report the chemical investigation of a previously unstudied secretion of a pentatomid bug, Aspavia brunna. The combined gas chromatography -mass spectrometry provides an excellent method for the study of the secretions of insects. We have utilized this technique and our results are summarized below.
Kristallstrukturen der selenid- bzw. sulfidverbrückten Gold(I)verbindungen [Se(AuPPh3)+
3]PF6
- und [S(AuPPh3)2] · CH2Cl2/Crystal Structures of the Selenide- and Sulphide-Bridged Gold(I) Complexes [Se(AuPPh3)3]+PF6
- and [S(AuPPh3)2] · CH2Cl2
Authors: Lensch Cornelia , Jones Peter G. , Sheldrick George M.
Published: February 2015

The Compound [S(AUPPh3)2] · CH2Cl2 was prepared from Ph3PAuCl and H2S in CH2Cl2 and characterised by X-ray structure determination [P21/c, a = 1851.6(4), b = 2225.1(6), c = 880.3(2) pm, β = 96.32(1)°, Z = 4, R = 0.053]. A constrained refinement of the light atom positions was necessary because of pseudosymmetry. Ph3PAuPF6 reacts with Se(Sn)(CH3)3)2 to give [Se(AuPPh3)3]+PF6- which was also characterised by X-ray methods [P1̄, a = 1539.5(6), b = 1800.5(7), c = 2289.5(9) pm, α = 89.35(3), β = 72.44(3), γ = 69.75(3)°, Z = 4, R = 0.061]. There are two formula units in the asymmetric unit. Both structures show short Au···Au contacts (ca. 300-340 pm).
Alkylvanadium(V)-Verbindungen Darstellung und NMR-spektroskopische Untersuchungen/Alkylvanadium(V) Compounds Synthesis and NMR Spectroscopic Studies
Authors: Preuss Fritz , Ogger Lothar
Published: February 2015

The compounds Li[nC4H9VO(OtC4H9)3], Me3SiCH2V(OtC4H9)3, (CH3)2V(OSiMe3)2 and V(OtC4H9)4 have been prepared by reaction of esters VO(OR)3(R = tC4H9, SiMe3) with lithium alkyls. RVO(OtC4H9)2 species are not formed by direct alkylation of VO(OtC4H9)3 with LiR; albeit in small yields, these compounds (R = CH3, CH2SiMe3) can be synthesized however from VO(OtC4H9)2Cl. The 51V, 1H and 13C NMR spectra of the vanadium(V) and vanadium(IV) compounds are discussed; the constants of 51V, 1H and 51V, 13C coupling have been determined.
Zintlphasen mit komplexen Anionen: Zur Kenntnis von Ca3AlAs3 und Ba3AlSb3/Zintl Phases with Complex Anions: On Ca3AlAs3 and Ba3AlSb3
Authors: Cordier Gerhard , Savelsberg Gerhard , Schäfer Herbert
Published: February 2015

The new compound Ca3AlAs3 crystallizes in the orthorhombic system (space group: Pnma) with

a = 1221.2(3) pm, b = 420.1(2) pm, c = 1343.4(4) pm.

In the structure there are AlAs4-tetrahedra connected by common corners to „Einereinfach" chains.

The new compound Ba3AlSb3 crystallizes in the orthorhombic system (space group: Cmca) with

a = 2113.3(10) pm, b = 719.4(5) pm, c = 1400.9(8) pm.

AlSb4-tetrahedra are connected by common edges to isolated Al2Sb6 groups. According to the compositions and structures both compounds belong to the Zintl-phases.
Zur Rutilverwandtschaft: Zur Kenntnis von LiSrFeF6[1]/On the Knowledge of LiSrFeF6
Authors: Fleischer Th. , Hoppe R.
Published: February 2015

Hitherto unknown LiSrFeF6 was obtained by heating mixtures of binary fluorides [LiF + SrF2 + FeF3; Li:Sr:Fe = 1:1:1] under argon [Au tubes, 500 °C, 2 d or 650 °C, 14d] as a colourless powder or colourless single crystals. LiSrFeF6 crystallizes monoclinicly in P21/c-C5
2h with a = 5,2972(4), b = 8,7989(8), c = 10,2257(7) Å, β = 92,212(8)°, Z = 4; drö = 3,69 und dpyk = 3,66 g · cm-3, positions are given in the text, R = 9,16% (Rw = 6,83%) for hkl (Mo-Ka, 4-circle diffractometer data).
Zur Rutilverwandtschaft: Über neue Fluoride des Typs LiMIIMIIIF6 mit MIII = Co, Ni und MII = Mg, Ca, Sr, Ba, Ni, Cu, Zn, Cd [1]/On New Fluorides of the Type LiMIIMIIIF6 with MIII = Co, Ni and MII = Mg, Ca, Sr, Ba, Ni, Cu, Zn, Cd [1]
Authors: Fleischer Thomas , Hoppe Rudolf
Published: February 2015

By pressure fluorination in monel autoklaves samples of LiCuCoF6 (rutile type structure), LiMgCoF6, LiNiCoF6 and LiZnCoF6 (trirutile type structure), LiCdCoF6, LiCaCoF6, LiCaNiF6 and LiSrNiF6 (LiCaAlF6-type [2] structure), LiSrCoF6 (LiSrFeF6-type structure [3]) and LiBaCoF6 (LiBaCrF6-type structure [4]) were synthesised for the first time. The Madelung Part of Lattice Energie, MAPLE, is studied and discussed. By magnetic measurements we obtained new information on the structure of fluorotrirutile.
Fehlordnung von Kationen und Kristallwasser bei kubischen Alkalitetrabromo- und -iodothallaten(III)/Disorder of Cations and Water Molecules in Cubic Tetrabromo- and -iodothallates
Authors: Rotter Heinz W. , Thiele Gerhard
Published: February 2015

Tetrabromo- and -iodothallates(III) of the alkali cations crystallise from aqueous solutions as cubic hydrates MTlX4·nH2O (M = Li, Na, K, Rb, Cs, NH4; X = Br, I; n = 1-2). The tetraiodothallates retain their cubic structure on dehydratisation, while the tetrabromothallates undergo structural changes. The X-ray structure analyses of RbTlBr4 · H2O, NH4TlBr4 · 2H2O and KTlBr4 · 2H2O (-50 °C) showed that these compounds consist of a three-dimensional framework of TlBr4 tetrahedra and MBr12 ikosahedra which reminds of zeolites. In cavities of this framework 2/3 of the alkali cations and the crystal water molecules are accommodated in a disordered manner.
Strukturuntersuchungen an Vierringsystemen, III* Kristall- und Molekülstrukturen von trans-2.4-Bis(trimethylsilyl)-2.4-dihydro- 1.3-dithietan-1.1.3.3-tetroxid, 2.2.4.4-Tetramethyl-3-pyrrolidinocyclobutanon und 2.2.4.4-Tetramethyl-1-phenyl-3-pyrrolidinoeyelobutanol/Structural Investigations on Four-Membered Ring Systems, III* Crystal and Molecular Structures of trans-2,4-Bis(trimethylsilyl)-2,4-dihydro-1,3-dithietane-1,1,3,3-tetroxide, 2,2,4,4-Tetramethyl-3-pyrrolidinocyclobutanone and 2,2,4,4-Tetramethyl-1-phenyl-3-pyrrolidinocyclobutanol
Authors: Balbach Barbara , Alt Reinhold , Ziegler Manfred L.
Published: February 2015

The molecular structures of the title compounds have been determined by X-ray methods. In the bis(trimethylsilyl) substituted dithietane the (CH3)3Si groups are in trans position; the C2S2-ring is planar. In the cyclobutanone the pyrrolidine group occupies an equatorial position, as does the phenyl group in the cyclobutanol. In the latter the hydroxyl group is trans to the pyrrolidine ring. The four-membered carbon rings are folded.
Synthesen und Reaktionen von schwefelkoordinierten Ruthenium-Komplexen [1]/Syntheses and Reactions of Sulfur Coordinated Ruthenium Complexes [1]
Authors: Sellmann Dieter , Böhlen Elmar
Published: February 2015

The syntheses and reactions of sulfur coordinated ruthenium centers with CO, PR3, (R = Me, Ø), N2H4 and N2 are investigated. Reaction of [Ru(CO)3(THF)Cl2] with lithium-o-methylthiobenzenethiolate yields cis-[Ru(CO)2(CH3S-C6H4-S)2], with Li2-o-benzenedithiolate the cis-[Ru(CO)2(C6H4S2)2]2--ion is obtained, which can be isolated either as the NMe4 salt or reacted further with 1,2-C2H4Br2 to give cis-[Ru(CO)2dttd], (dttd2-= 2,3,8,9-Dibenzo-1,4,7,10-tetrathiadecane2-). In all three complexes the CO ligands are relatively inert to substitution; refluxing of [Ru(CO)2(C6H4S2)2]2- in EtOH in the presence of excess PMe3, however, and subsequent alkylation with 1,2-C2H4Br2 yields [Ru(CO)PMe3(dttd)]. [Ru(PMe3)2dttd] is obtained from [Ru(PMe3)4Cl2] and Li2-dttd, the synthesis of which is also described. In [Ru(PMe3)2(dttd)] the PMe3 ligands are inert, but in [Ru(PØ3)2(dttd)] one PØ3 ligand is easily substituted by CO or N2H4 yielding [Ru(CO)(PØ3)dttd] or [Ru(N2H4)(PØ3)dttd] respectively; [Ru(PØ3)2(dttd)] is obtained from [RU(PØ3)3Cl2] and H2-dttd. The complexes are characterized by elemental analyses, IR, 1H NMR and mass spectroscopy.
Diazadiphosphetidin- Platin (0) - Komplexe/Diazadiphosphetidine Platinum(0) Complexes
Authors: Scherer Otto J. , Krieger Klaus-Dieter
Published: February 2015

The reaction of Pt(COD)2 with cis-[RPNCR3]2 (1), R = CH3, affords the two-coordinate platinum(0) complex PtL2 (2) (L = diazadiphosphetidine 1). In benzene solution PtL2, Pt2L3 (3) and L are in equilibrium. 2 and diphenylacetylene or fumaric acid dinitrile give the platinum diazadiphosphetidine complexes L2Pt(PhCCPh) (4) and L2Pt[H(NC)CC(CN)H] (5), L = 1.
Aryl(halogeno)bis(triphenylphosphan)platin(II)-Verbindungen. Synthesen und cis-trans-Isomerisierungen/Aryl(halogeno)bis(triphenvlpliosphane)platinum(II) Compounds Syntheses and cis-trans Isomerizations
Authors: Ertl Josef , Grafl Dieter , Brune Hans Albert
Published: February 2015

The syntheses of the platinum-organic compounds cis-[Pt(PPh3)2(X-C6H4)Cl] (X = H, 3-H3C-, 3-H3CO-, 4-H3C-, 4-H3CO-) and cis-[Pt(PPh3)2(X-C6H4)Br] (X = H, 3-H3C-, 3-H3CO-, 3-(H3C)2N-, 4-H3C-, 4-H3CO-) are described; their thermal isomerization in crystalline phase are studied and the resulting trans-isomers characterized.
Metall-Schwefeldioxid -Komplexe/ Metal Sulfur Dioxide Complexes
Authors: Hoppenheit Reinhard , Isenberg Wilhelm , Mews Rüdiger
Published: February 2015

The preparation of sulfur dioxide complexes M(SO2)2(AsFe) (1 a-1 g M = Mn, Fe, Co, Ni, Cu, Zn, Mg) is possible in liquid SO2 (a) by oxidation of the metals with AsF5, (b) by metathesis of metal halides, e.g. NiBro, with AgAsF6, (c) by the reaction of metal fluorides, e.g. ZNF2, with AsF5. The spectroscopic properties of these complexes are discussed and the structure of [Mg(SO2)2(AsF6)2]n (1 g) is reported.
Die Kristallstrukturen von PPh4[SnCl3] und PPh4[SnBr3]/ The Crystal Structures of PPh4[SnCl3] and PPh4[SnBr3]
Authors: Müller Ulrich , Mronga Norbert , Schumacher Christina , Dehnicke Kurt
Published: February 2015

PPh4[SnCl3] and PPh4[SnBr3] were prepared by reaction of PPh4X with SnX2 in CH2X2 solutions (X - Cl, Br). The vibrational spectra of the [SnX3]⊖ ions show three SnX3 stretching frequencies, which is caused by deviations from the ideal C3v symmetry. In the crystal structure determinations these deviations show up by slightly different Sn-X bond lengths which are explained by differing hydrogen bridges to phenyl-H atoms. The isotypic crystal structures of both compounds were determined and refined from X-ray diffraction data (R values: 0.042 and 0.034). Although triclinic (space group P1̄), the structures are closely related to the tetragonal AsPh4[RuNCl4] structure type. Very pure SnBr2 is prepared by the reaction of PPh4[SnBr3] with AlBr3 in CH2Br2 solution.
Darstellung und Kristallstruktur von Kupfer(I)tetrachloroaIuminat, CUAlCl4/ Preparation and Crystal Structure of Copper(I) Tetrachloroaluminate, CuAlCl4
Authors: Hildebrandt Kerstin , Jones Peter G. , Schwarzmann Einhard , Sheldrick George M.
Published: February 2015

Crystalline CuAlCl4 was prepared from CuCl and AlCl3 in a quartz tube at 533 K. The crystal structure was determined [P4̄2c, a = 543.0(1), c = 1009.6(1) pm, Z = 2, Rw =0.034 for 345 reflections]. The chlorine atoms form a distorted cubic close-packed lattice, with copper and aluminium each occupying an eighth of the tetrahedral holes (site symmetries 4̄ and 222, respectively).
Schwefel-Stickstoff-Verbindungen, XI. Elektrochemische Untersuchung einiger aromatisch substituierter Schwefeldiimide/ Sulfur-Nitrogen Compounds, XI. Electrochemical Investigations on Some Aromatic Substituted Sulfurdiimides
Authors: Brands Gilbert , Golloch Alfred
Published: February 2015

The electrochemical reduction and oxidation of sulfurdiimines R1-NSN-R2 (R1,2 = C6H5, C6F5, C6H5S, C6F5S) in organic solvents is studied. Both reactions proceed in the sulfur-nitrogen system in a one-electron step. The influences of the substituents are, however, different.
Metallkomplexe mit Tetrapyrrol-Liganden, XXVIII. Mononukleare Nitridomangan(V)-Porphyrine: die ersten Mangan-Stickstoff-Dreifachbindungen/ Metal Complexes with Tetrapyrrole Ligands, XXVIII. Mononuclear Nitridomanganese(V) Porphyrins: the First Manganese Nitrogen Triple Bonds
Authors: Buchler Johann W. , Dreher Christine , Lay Kiong Lam
Published: February 2015

The first complexes containing a manganese-nitrogen triple bond, nitrido(octaethylporphinato) manganese(V) [MnN(OEP)]** and nitrido[meso-tetra(p-tolyl)porphinato]manganese( V) [MnN(TTP)], are prepared by hypochlorite oxidation of the corresponding methoxomanganese( III) porphyrins, Mn(OEP)OMe and Mn(TTP)OMe, in the presence of ammonia. The red, pentacoordinated, diamagnetic species are identified by UV/VIS-, IR-, 1H NMR, and mass spectra. While the isoelectronic oxochromium(IV) or oxomolybdenum( IV) porphyrins behave as weak oxidants or reductants, respectively, the nitridomanganese( V) unit in the square pyramidal environment is chemically remarkably stable.
Studien zum Vorgang der Wasserstoffübertragung, 63. Elektrochemische Herstellung einiger Amalgame und Bestimmung ihrer Potentiale/ Studies on the Occurrence of Hydrogen Transfer, 63. Electrochemical Preparation of Some Amalgams and Measurement of the Potentials
Authors: Horner Leopold , Schmitt Rolf-Erhard
Published: February 2015

The amalgams of lithium, sodium, potassium, barium and zinc were prepared electrochemically (potentiostatic and galvanostatic, see Tables I and II). The potentials of these were measured in acetonitrile, THF and DMF, using the corresponding Perchlorate (Li, Na, K, Ba, Zn) or tetrabutylammonium perchlorate as electrolyte and a standard calomel olektrode (SCE) (Table III). In the case of the lithium amalgam, the dependence of the potential on the lithium content was studied (Table IV). The potential moves slightly to more positive values on dilution, dilution by a factor of 100 producing a shift of only ca. 100 mV.
Eliminierung von Aceton und Bildung von protoniertem Aceton bei der chemischen Ionisation von [2.2.6.6]-Tetramethylcyclohexanon/ Elimination of Acetone and Formation of Protonated Acetone from [2,2,6,6]-Tetramethylcyclohexanone under the Condition of Chemical Ionisation
Authors: Wolfschütz Roland , Franke Wilfried , Heinrich Nikolaus , Schwarz Helmut , Blum Wolfgang , Richter Wilhelm J.
Published: February 2015

By means of appropriately D and 13C labelled precursors it is shown that the proton catalysed degradation of [2,2,6,6]-tetramethyl cyclohexanone {e.g. elimination of acetone and formation of protonatecl acetone from [MH]+) proceeds via two distinct pathways. The energetically favoured one (pathway A, Scheme 1) involves a sequence of [1,2]-methyl migration, ring contraction and methyl migration, whereas the energetically less attractive path B commences with a Wagner-Meerwein ring contraction, followed by hydroxyl and methyl migration. Semi-empirical quantum mechanical calculations (MNDO) are em-ployed to explore computationally relevant parts of the potential energy surface. The syntheses of the specifically 13C labelled title compounds (1 a, b) are described in detail.
Additionsverbindungen von Methylhalogensiianen und Pyridin bei tiefen Temperaturen/ Addition Compounds of Methylhalogenosilanes and Pyridine at Low Temperatures
Authors: Hensen Karl , Busch Reiner
Published: February 2015

By analyzing the melting point diagrams of some methylhalogenosilane-pyridine systems the existance of the stable addition compounds CH3SiCl3 · 2 py, CH3SiBr3 · 2 py, (CH3)2SiBr2 · py, (CH3)3SiBr · py was proved. In the systems (CH3)2SiCl2/py and (CH3)2SiBr2/py unstable 1:2-complexes are also found. (CH3)3SiCl forms no complexes with pyridine.
Phosphonyl- und Phosphinyl-triazene. Elektrophile Substitutionsreaktionen mit Benzol/ Phosphonyl- and Phosphinyl-triazenes. Electrophilic Substitution Reactions with Benzene
Authors: Kreher Richard , Halpaap Reinhard
Published: February 2015

The reaction of phosphonyltriazenes with benzene in the presence of aluminiumchloride is involved with the elimination of nitrogen and followed by electrophilic substitution of benzene. The arylation reaction obviously proceeds via the intermediate formation of arene diazonium ions. Phosphinyltriazenes display the same chemical behaviour.
Die Kristall- und Molekülstruktur von Tris(dimethylamino)boran / The Crystal and Molecular Structure of Tris(dimethylamino)borane
Authors: Schmid Günter , Boese Roland , Bläser Dieter
Published: February 2015

Tris(dimethylamino)borane, X-ray The crystal and molecular structure of tris(dimethylamino)borane, a liquid at room temperature, has been determined by single-crystal X-ray diffraction methods at - 116°C. The single-crystal growth was accomplished by means of a miniature zone melting process on the diffractometer. The structure data are compared with those of other aminoboranes.
Übergangsmetall-Carbin-Komplexe, LXXII [1]. Reaktionen von trans-Bromotetracarbonyl(phenylcarbin)chrom mit Lithiumthiokresolat und Lithiumselenophenolat / Transition Metal Carbyne Complexes, LXXII [1]. Reactions of trans-Bromotetracarbonyl(phenylcarbyne)chromium with Lithium Thiocresolate and Lithium Phenylselenolate
Authors: Roll Werner , Fischer Ernst Otto , Neugebauer Dietmar , Schubert Ulrich
Published: February 2015

The reaction of trans-bromotetracarbonyl(phenylcarbyne)chromium (1) with lithium phenylselenolate and subsequent protonation with aqueous hydrochloric acid leads to (CO)5Cr[Se2(C6H5)2] (3) and (CO)4Cr(μ-SeC6H5)2Cr(CO)4 (4). From 1 and lithium 4-methylphenylthiolate (CO)5CrC(C6H5)SC6H4CH3 (5) and (CO)5CrS(C2H5)(4-CH3C6H4) (6) are obtained, if triethyloxonium tetrafluoroborate is used instead of hydrochloric acid. The analoguous reaction of 1 with lithium phenylselenolate yields the seleno ether complex (7). Reaction conditions, properties, spectroscopic data and the results of an X-ray structure determination of the binuclear complex (4) are reported.
Effects of Through-Conjugation on the Molecular Structure of p-Nitroaniline [1]
Authors: Colapietro Marcello , Domenicano Aldo , Marciante Clara , Portalone Gustavo
Published: February 2015

A new X-ray diffraction study of p-nitroaniline shows that through-conjugation has highly significant effects on the geometry of the molecule, as compared to aniline and p-nitrobenzoic acid. The effects include a moderate decrease of the internal angles of the ring at substituted carbons, with respect to values derived by superimposing independent angular distortions from each substituent.
Röntgenstrukturbestimmung von AlCl3-Pyridin-Addukten: Der strukturelle Aufbau im trans-Dichlorotetrakis(pyridin)aluminium(III)- Tetrachloroaluminat(III) und im Trichlorotris(pyridin)aluminium(III) / X-ray Diffraction Study of AICl3-Pyridine Adducts: The Crystal Structure of trans-Dichlorotetrakis(pyridine)aluminium(III)tetrachloroaluminat(III) and of Trichlorotris(pyridine)aluminium(III)
Authors: Pullmann Peter , Hensen Karl , Bats Jan W.
Published: February 2015

Crystals of [Al(C5H5N)4Cl2][AlCl4] are orthorhombic, Pna21, Z = 4, a = 18.522(7), b = 15.141(5), c = 9.593(3) Å, V = 2690(2) Å3 , Dc = 1.440 g/cm3 . The structure has been solved from 5968 diffractometer measured intensities and refined by full-matrix least squares to Rw(F) = 0.032. The crystal structure shows the complex to be trans-dichloro-tetrakis(pyridine)aluminium(III) tetrachloroaluminat(III). The mean trans Al-Cl-and trans Al-N-distances in the octahedron are 2.279(3) and 2.070(4) Å, respectively. Crystals of Al(C5H5N)3Cl3 are monoclinic, P21/c, Z = 4, a = 7.261(2), b = 29.961(4), c = 8.624(1) Å, β = 98.12(2)°, V -1857(1) Å3 , DC = 1.326 g/cm3 . The structure has been solved from 4707 diffractometer measured intensities and refined to Rw(F) = 0.028. The crystal structure shows octahedral complexes AlCl3·3 (C5H5N) with trans geometry. The Al-N-distance trans to chlorine (2.096(2) Å) is significantly longer than the two other Al-N-distances (mean 2.072(2) Å).
Darstellung und Struktur von Dimesitylzinnoxid / Synthesis and Structure of Dimesityltinoxide
Authors: Weber U. , Pauls N. , Winter W. , Stegmann H. B.
Published: February 2015

Trimesityltin bromide reacts with concentrated aqueous ammonia to give trimesityltin hydroxide. This compound eliminates mesitylen and yields dimesityltin oxide. The product was investigated bv 13C NMR, mass spectroscopy and X-ray diffractions. Di-mesityltinoxide crystallizes in the space group P21/w with a = 25.38(1) Å, b = 12.525(5) Å, c= 32.91(1) Å, β= 91.37(3)° and two molecules in the asymmetric unit (Z=8). The R-factor is 0.049 for 4688 symmetry-independent reflections. The trimeric molecules have six-membered tin-oxygen heterocycles in a twist conformation.
Synthesen mit Nitrilen, LXV [1]. Pyrazolo [3,4-b] pyridine und Polymethine aus Benzoylacetonitril-hydrazonen und Tetracyanethylen / Syntheses with Nitriles, LXV [1]. Pyrazolo[3,4-b]pyridines and Polymethines from Benzoylacetonitrile-hydrazones and Tetracyanoethylene
Authors: Schmidt H. W. , Gfrerer G. , Junek H.
Published: February 2015

Condensation of benzoylacetonitrile (1a) and benziminoacetonitriles (1b, c), resp., with tho hydrazines 2a-f leads to benzoylacetonitrile-hydrazones (3a-i), which react with tetracyanoethylene to give pyrazolo[3,4-b]pyridines (6a-d) and polymethines (7a, b, 8), resp.
Cyclopropyl- und Alkyl-Carbanionen mit Akzeptor-Substituenten in α-Stellung. Eine MO-Studie zur Konfiguration der Anionen und Acidität der entsprechenden CH-Säuren / Cyclopropyl and Alkyl Carbanions with Acceptor Substituents in α-Position. An MO Study of the Configuration of the Anions and the Acidity of the Corresponding CH Acids
Authors: Wagner Hans-Ulrich , Boche Gemot
Published: February 2015

a-Hydrogens a-Hydrogens of R-C ≡ C-and N ≡ C-substituted cyclopropanes are more acidic than their open chain analogs, as expected from the higher acidity of cyclopropane versus propane. In the case of the carbonyl substituted species, however, this order is reversed. Furthermore, in H/D exchange reactions of optically active compounds, only cyclopropyl cyanides retain their configuration; aliphatic and cyclopropyl ketones exchange and racemize essentually at the same rate.

This behaviour has been rationalized qualitatively in the following manner: RC = C-and N ≡ C-substituents stabilize a negative charge mostly inductively; on the other hand, with carbonyl groups, delocalisation of the negative charge (resonance) is more important than the inductive effect. Thus the unfavourable configuration (I-strain) of the planar cyclopropyl enolate anions is in agreement both with the low acidity of the corresponding cyclopropanes and with the loss of optical activity in H/D-exchange reactions.

In order to put this explanation on a more quantitative basis, we calculated the relative proton affinities of isopropyl-and cyclopropyl-carbanions by means of the ab-initio STO-3G method. In the case of X = H, CF3 and C ≡ N, the cyclic anion (CH2)2C⊖X is more stabilized by the substituent X than in the anion (CH3)2C⊖X; with X = CHO, COOH and NO2 the order is reversed. Cyclopropyl anions should have a pyramidal configuration with X = H, CF3, C ≡ N and NO2, which indicates a strong inductive effect also of the nitro group.

In summary: STO-3G calculations support the qualitative explanations of the experimental results with regard to the acidities of substituted cyclopropanes.
Heterocyclische Siebenring-Verbindungen, XXIY [1]. Photochemische Reaktion von 2-Methyl-4-phenyl-1-benzothiepinen / Heterocyclic Seven-membered Ring Compounds, XXIV [1]. Photochemical Reaction of 2-Methyl-4-phenyl-1-benzothiepins
Authors: Hofmann Hans , Heidrich Rainer
Published: February 2015

The photoreaction of the 2-methyl-4-phenyl-1-benzothiepins 1a und 1b leads first to the not isolated primary pliotoproducts 2 a and 2 b. These were entirely transformed to the secondary pliotoproducts 3a and 3b in the course of the irridation.
Alkaloide aus Catharanthus roseus-Zellkulturen, III [1] / Alkaloids from Catharanthus roseus Tissue Cultures, III [1]
Authors: Kohl Werner , Witte Barbara , Höfle Gerhard
Published: February 2015

From the methanol extract of Catharanthus roseus tissue cultures sitsirikine (2), isositsirikine (3), dihydrositsirikine (4), yohimbine (5), 3-iso-19-epiajmalicine (6), pleio-carpamine (7), antirhin (8) and two up to now unknown alkaloids have been isolated in addition to the compounds previously found in the hexane extract. The structures belonging to lieteroyohimbane, vallesiachotamine, corynanthe and related types were deduced by UV, NMR and mass spectroscopy.
Die Kristallstruktur von Hexa-μ-chloro-μ4- oxo - tetrakis [hexamethy lentetramin - kupfer(II)] , [CU4Cl60(C6H12N4)4] , einem Kupfer(II)-Komplex mit Berylliumoxoacetat-ähnlicher Struktur / The Crystal Structure of Hexa-μ-chloro-μ4- oxo-tetrakis [hexamethylenetetraminecopper- (II)], [Cu4Cl6O(C6H12N4)4], a Copper(II) Complex with a Structure Related to that of Beryllium Oxoacetate
Authors: Pickardt Joachim , Rautenberg Norbert
Published: February 2015

By reaction of solutions of CuCl2·2H2O and hexamethylenetetramine, C6H12N4, in acetone, a complex [Cu4Cl6O(C6H12N4)] could be obtained as single crystals. An X-ray analysis shows that the complex has a structure related to that of basic beryllium acetate. An oxygen atom is tetrahedrally surrounded by four cop-per atoms which, together with six chlorine atoms, form an adamantane-like core. Each copper atom is bonded via a nitrogen atom to a hexamethylenetetramine molecule.
Zur Darstellung und Kristallstruktur von β-NbO2 / Synthesis and Crystal Structure of β-NbO2
Authors: Schweizer H.-J. , Gruehn Reginald
Published: February 2015

By using chemical transport reactions with various transporting agents (HgCl2, NbCl5, Nb3O7Cl) a slightly substoiehiometric NbO2-phase, β-NbO2, was obtained from samples with O/Nb ∼ 1.5 (source; T > 1373 K) and with deposition temperatures > 1273 K (sink). The rango of composition of β-NbO2 was found to exist from NbO1.990 to NbO1.998.

The structure of the tetragonal, column-shaped black crystals was determined by X-ray diffraction. It crystallizes tetragonally in the space group I41 with lattice constants a = 9.693(3) Å, c = 5.985(1) Å and Z = 10 formula units.

The crystal structure of β-NbO2 is shown to be a deformed rutile type. As in α-NbO2 the Nb-atoms are grouped in pairs. However, both oxides are different with respect to their long-range order.
Die Reduktion von Triphenylphosphan-Derivaten zu ihren Radikalanionen und zum Dibenzophosphol-Radikaldianion [1] / The Reduction of Triphenylphosphane Derivatives to their Radical Anions and to the Radical Dianion of Dibenzophosphole [1]
Authors: Kaim Wolfgang , Hänel Peter , Bock Hans
Published: February 2015

Triphenylphosphane 1, its oxide 2 and sulfide 3 undergo one-electron reduction at a mercury cathode in DMF to yield the corresponding radical anions. ESE analysis of the paramagnetic species is facilitated by deuteration and suggests a pyramidal geometry of the radicals. Reduction with potassium metal in DME at low temperature yields also radical anions for 2 and 3. The phosphane 1, however, reacts under phenyl cleavage and potassiumphenyl-assisted ring closure to the dianion of 5H-dibenzophosphole 4. This radical 4· ⊖⊖ is also obtainod by alkali metal reduction of P-phenyldibenzophosphole o, and its spin distribution is compared to iso-.-π-electronic radicals containing CH, N, O, S, or Se links instead of the phosphorus atom.
N-Chloramidophosphate / N-Chlorophosphoramidates
Authors: Drewelies Kurt , Pritzkow Hans
Published: February 2015

The structure of the known compound O,O-Diphenyl-N-chlorophosphoramidate has been determined by X-ray diffraction. It consists of dimers, in which the monomers are connected by N-H···O hydrogen bonds. The O,O-Diethyl-N-chlorophosphoramidate homologue can be synthesized by various methods. At room temperature it is part of an equilibrium mixture with O,O-Diethyl-phosphoramidate and O,O-Diethyl-N,N-dichloro-phosphoramidate.
Resonance Raman and Electronic Spectra of Mixed Valence Compounds with Ni(II)---X-Ni(IV) and Ni(II)---X-Pt(IV) Chains (X = Cl or Br)
Authors: Papavassiliou G. C. , Layek D.
Published: February 2015

The resonance Raman and electronic spectra of compounds Ni(en)2X3, Ni(dapn)2X3 etc. and of compounds [Ni(en)2Pt(en)2X2](ClO4)4 (where X = Cl or Br) show that those are mixed valence compounds with a metal halide chain (en = 1,2-diaminoethane, dapn = 1,2-diaminopropane).
195Pt-NMR-Messungen an stereoisomeren Chloro-Bromo-Platinaten(rV) / 195Pt NMR Studies on Stereoisomeric Chloro Bromo Platinates(IV)
Authors: Pregosin P. S. , Kretschmer M. , Preetz W. , Rimkus G.
Published: February 2015

195Pt NMR spectra for the pure anionic complexes [PtClnBr6-n]2- have been measured in acetone solution. The isomerization reactions cis-[PtClnBr6-n]2- → trans-[PtClnBr6-n]2-, n = 2, 4 and fac-[PtCl3Br3]2- → mer-[PtCl3Br3]2- are slow on the NMR time scale and these slow kinet ics allow an unambiguous assignment of the 195Pt signals. The cis and fac complexes are found at slightly lower field (12-15 ppm) than their trails and mer counter­parts. There is a linear correlation of δ 195Pt with the sum of the Allred-Rochow electronegatives of the halogen atoms.
Derivatives of NPCl2(NSOCl)2 and (NPCl2)2NSOCl, Part XX [1]. Reactions of Some Inorganic Ring Systems with N,N′ -Dimethylethylenediamine
Authors: Ruiter Barteld de , Kuipers Geert , Bijlaart Jan H. , Grarnpel Johan C. van de
Published: February 2015

Reactions of the ring systems (NPCl2)3, (NPCl2)2NSOX, and NPCl2(NSOX)2 (X = Cl, Ph) with N,N′-dimethylethylenediamine lead to mono-, bis-, and tris(spirocyclic) com­pounds as the only characterizable products. The 1H and 31P NMR parameters are re­ported and briefly discussed.
Zweikernige und dreikernige Carbonyleisenkomplexe mit 1.2-und 1.3-Dithiolatobrückenliganden / Dinuclear and Trinuclear Carbonyliron Complexes Containing 1,2-and 1,3-Dithiolato Bridging Ligands
Authors: Winter Andreas , Zsolnai Laszlo , Hüttner Gottfried
Published: February 2015

The reactions of 1,2- and 1,3-dithioles, HSRSH, with Fo3(CO)12 give the dinuclear compounds Fe2(CO)6(SRS) in good yields. With R = C2H4 or R = C3H6 the trinuclear compounds (CO)3Fe(SRS)Fe(CO)(SRS)Fe(CO)3 containing an open Fe3 chain are obtained.
Triorganozinn- und Triorganobleiderivate von N-Benzoyl- und N-Formylglycin / Triorganotin and Triorganolead Derivatives of N-Benzoyl-and N-Formylglycine
Authors: Roge Gerhard , Huber Friedo , Silvestri Arturo , Barbieri Renato
Published: February 2015

Triorganotin and -lead derivatives of X-benzoylglveine (BzGlyH) and N-formylglycine (ForGlyH), R3MBzGly and R3MForGly (M = Sn; R = Me, Ph. M = Pb; R = Ph) have been prepared from R3MOH and BzGlyH or ForGlyH, respectively. According to spectro­scopic data the Me3Sn groups are essentially planar; molecules of R3SnForGly are bridged by unidentate carboxylate groups and formyl-C = O groups in the solid state, while Ph3PbForGly and benzoylglycinates are bridged by bidentate carboxylate groups. NH does not coordinate to M. Pentacoordination and a polymeric nature in the solid state is also indicated by Mößbauer data of Me3SnForGly and Me3SnBzGly. In solution all compounds are monomeric.
Fluoreszenz von Distyrylbenzolen und Distyrylstilbenen / Fluorescence of Distyrylbenzenes and Distyrylstilbenes
Authors: Erckel R. , Frühbeis H.
Published: February 2015

Absorption, corrected emission spectra, fluorescence quantum yields, and preparation are reported for distyrylbenzene, distyrylstilbene and substituted derivatives. The Stokes shifts are measured in three solvents and correlated with quantum chemical calculations.
Some Extensions of von Braun (BrCN) Reaction on Organic Bases, Part III
Authors: Siddiqui Salimuzzaman , Begum Sabira , Siddiqui Bina S.
Published: February 2015

In continuation of studies on some extensions of von Braun BrCN reaction on organic bases, work on diisobutylamine and di-2-butylamine, has led to various substituted ureas and N-imino-ethyl ether derivatives. In contrast to previous observations, reduction of their cyanamides with zinc/HCl gave the amido derivatives instead of diamines.
Kristallstrukturell von Verbindungen A2X2 (A=S, Se; X=Cl, Br) / Crystal Structures of Compounds A2X2 (A=S, Se; X=Cl, Br)
Authors: Kniep Rüdiger , Körte Lutz , Mootz Dietrich
Published: February 2015

The crystal structures of compounds A2X2 (A=S, Se; X=Cl, Br) contain molecules X-A-A-X with dihedral angles between 83.9° and 87.4°. Three different types of molecular packing are realized: S2CI2, S2Br2 (α-Se2Br2) and β-Se2Br2(Se2Cl2). Details of molecular geometries as well as crystal structures are discussed.
Derivatives of NPCl2NSOCl)2 and (NPCl2)2NSOCl, Part XXI [1]. The Synthesis of a Spiro Phosphazene Derivative of NPCl2(NSOPh)2
Authors: Winter Herman , Grampel Johan C. van de
Published: February 2015

The preparation of the spirocyclic compounds cis-and trans-NP[(NPCl2)2NCH3](NSOPh)2 from cis-and trans-NPCl2(NSOPh)2 is described as well as the synthesis of the inter-mediates. The 31P NMR data are discussed.
Darstellung und Kristallstruktur von Di-gold(III)bis(selenit)oxid, Au2(SeO3)2O / Preparation and Crystal Structure of Di-gold(III) Bis(selenite) Oxide, Au2(SeO3)2O
Authors: Jones Peter G. , Sheldrick George M. , Schwarzmann Einhard , Vielmäder Andreas
Published: February 2015

Au2(SeO2)2O was prepared from gold and excess selenic acid in a sealed tube at 533 K. The crystal structure [Pba2, a = 659.2(2), b = 1183.7(3), c = 399.8(1) pm, Z = 2,R = 0.087] was determined; gold atoms are bridged by oxide ions (lying on twofold axes) and selenite ions. The extended structure consists of polymeric layers parallel to the xy-plane. The light atom positions are inaccurate because of the presence of a heavy atom in a polar space group.
Monomere und dimere Oxotrihalogenoselenate(IV): Darstellung, Struktur und Eigenschaften von [As(C6H5)4]SeOCl3 und [N(C2H5)4]SeOCl3 / Monomerie and Dimeric Oxotrihalogenoselenates(IV): Preparation, Structure and Properties of [As(C6H5)4]SeOCl3 and [N(C2H5)4]SeOCl3
Authors: Krebs Bernt , Hucke Marita , Hein Michael , Schäffer Andreas
Published: February 2015

The monomeric SeOCl3- ion, which can be prepared as the tetraphenylarsonium salt from SeOCl2 and As(C6H5)4Cl, was structurally characterized by a low-temperature single crystal X-ray diffraction analysis. [As(C6H5)4]SeOCl3 is monoclinic, space group P21/c, with a = 9,332(3), b = 13,761(4), c = 18,985(6) Å, β = 110,97(3)° (at -135 °C), Z = 4; it contains a novel type of ψ-trigonal bipyramidal oxotrichloroselenate(IV) anion which is not associated to dimers or polymer chains as in known structures. The equatorial positions are occupied by doubly bonded oxygen (Se-O 1,601(3) Å) and by one Cl(Se-Cl 2,234(1) Å), the axial Se-Cl bonds (2,430(1) and 2,475(1) Å) being significantly longer. [N(C2H5)4]SeOCl3, which was obtained as crystals by oxidation of trichloroselenate(II), is triclinic, space group P1̄, with a = 10,607(3), b = 8,950(2), c = 8,862(2) Å, α = 119,79(2)°, β = 101,07(2)°, γ = 96,28(2)°, Z = 2. The X-ray structure analysis shows the anions to be present as centrosymmetric dimers Se2O2Cl6
2- like in the [P(C6H5)4]+ salt, with two tetragonal SeOCl4 pyramids linked through a Cl···Cl edge and the lone pairs trans to the axial Se-O bonds (1,589(4) Å). Se-Cl bond lengths are 2.270(1) and 2,351(2) Å (terminal); 2,698(1) and 2,920(1) Å (bridging). The results show that the nature of the reaction products of the Lewis acid SeOCl2 with halogenides as bases changes very sensitively with small variations in cations and environment. The vibrational spectra are discussed.
Anhydrous Chromium(III) Carboxylates: Reactions of CrO3 with Carboxylic Acid Anhydrides
Authors: Kapoor Ramesh , Sharma Ramneek
Published: February 2015

Chromium(VI) oxide reacts with excess of carboxylic acid anhydrides [(RCO)2O where R = CH3, C2H5, n-C3H7 and CHCl2] to give pure chromium(III) carboxylates. Their IR and 1H NMR spectra suggest the presence of two different types of carboxylate groups. Magnetic susceptibility and absorption spectra favour an octahedral geometry around Cr.
Kernresonanzspektroskopische Untersuchungen (1H-, 13C-, 31P-, 195Pt-NMR) an Alkinyl-Komplexen von PtII, PdII und NiII / Nuclear Magnetic Resonance (1H-, 13C-, 31P-, 195Pt-NMR)-Studies of Alkynyl Derivatives of PtII, PdII and NiII
Authors: Sebald Angelika , Wrackmeyer Bernd , Beck Wolfgang
Published: February 2015

The NMR parameters (1H, 13C, 31P, 195Pt) of compounds of the type cis- and trans- [M(C≡C-R)2(PR′3)2] (M = Ni, Pd, Pt) are reported. The chemical shifts δ13C (M-C≡C; R) and δ195Pt (together with UV data) indicate the presence of π-backbonding from the metal into π*C≡C the orbitals. This also explains some unusual features of the coupling constants J(≡13C1H), J(13C≡13C) and J(195Pt13C≡). The NMR parameters reflect an increase in the amount of π-backbonding for Pt < Pd < Ni.
Synthese und Strukturuntersuchungen von Iodocupraten(I): II. Diiodocuprate(I) RCuI2 mit isoherten Ketten 1
∞ [Cul4/2–]·R1 = N-Methylpyridinium, R2 = Dimethyl ( 3 - dimethylamino - 2 - aza - 2 -propenyliden ) ammonium [1] / Syntheses and Structure Analyses of Iodocuprates(I): II. Diiodocuprates(I) RCuI2 with Isolated Chains 1
∞ [CuI4/2–]; R1 = N-Methylpyridinium, R2 = Dimethyl(3-dimethylamino-2-aza-2-propenyliden) Ammonium
Authors: Hartl Hans , Mahdjour-Hassan-Abadi Farbod
Published: February 2015

N-Methylpyridinium-diiodocuprate(I), C6H8NCuI2 and dimethyl(3-dimethylamino-2-aza-2-propenyliden)ammonium-diiodocuprate(I), C6H14N3CuI2, are obtained by reacting Cu with C6H8NI3 or C6H14N3I3 in acetone. Both compounds are built up by the organic cations and chains of edge sharing tetrahedra1
∞[Cul4/2-]. The iodocuprate(I) anions are in intimate contact with the cations via intermolecular I···C interactions. Though nearly the same average Cu-I distance of 267.2 or 268.2 pm was found for both iodocuprate(I) anions there are different Cu-Cu distances (301-354 pm).