bluuebunny/crossref_metadata_2025 huggingface dataset:
Detection of Reactive Sulfur Molecules (S6, S7, S9, S∞) in Commercial Sulfur, in Sulfur Minerals, and in Sulfur Melts Slowly Cooled to 20 °C [1].
Authors: Steudel Ralf , Holz Birger
Published: March 2015

Quantitative analysis by high-pressure liquid chromatography shows that all commercial samples of elemental sulfur besides S8 contain traces of S7 (up to 0.56%) and in some cases also S6, S9 , and polymeric sulfur (S∞). Pure S8 can be obtained by recrystallization from CS2 . Elemental sulfur minerals also quite often contain traces of S7 (up to 0.3%). Since neither irradiation by daylight at 20 °C nor heating to 90 °C for 41 days did convert α-S8 into S7 , the reactive sulfur molecules Sn (n≠8) are believed to origin from liquid or gaseous sulfur which are known to be complex equilibrium mixtures of many Sn species. Sulfur melts slowly cooled (within 0.6 to 145 h) from 122 to 20 °C in fact contain S7 (minimum 0.2%) and at cooling rates of <24 h also other non-S8 molecules. Solid solutions of S7 in α-S8 have also been prepared by cocrystallization of the compounds from CS2. In contrast to pure α-S8, these solid solutions are pale-yellow at 77 K, and the implications of these findings for the surface composition of Jupiter’s satellite Io and for the mechanical properties of “formed sulfur” (Prills, Rotoform, Slates, etc.) are discussed.
Nachweis von Corticosteroiden im Fett von Dachs und Murmeltier / Detection of Corticosteroids in Fat of Badger and of Alp-Marmot
Authors: Wagner H. , Nusser D.
Published: March 2015

In our search for the antiinflammatory activ principles of fat of badger and alp-marmot, used in folk-medicine as remedies against rheumatism and arthritis, eight known corticosteroids have been detected and identified in the lipophilic fraction of body fats of both animals. Enrichment and detection succeeded by using TLC, straight phase HPLC with diode array equipment, HR-GC on OV-1 capillary columns and GC/MS of the methyloxime-trimethylsilylated steroids. The amount of the detected steroids ranges from 30-40 mg/kg. The whole antiinflammatory activity of the fat, as measured in the rat paw edema test, results from these and further hitherto unidentified cortico-steroids.
Übergangsmetall-Carbin-Komplexe, XC. Synthese neuer, siebenfach-koordinierter, kationischer Carbin-Komplexe des Wolframs in einer höheren Oxidationszahl / Transition Metal Carbyne Complexes, XC. Synthesis of New, Seven Coordinated, Cationic Tungsten Carbyne Complexes in a Higher Oxidation State
Authors: Filippou Alexander Constantin , Fischer Ernst Otto , Guido Helmut
Published: March 2015

The reaction of (I)3(CO)L2W≡CNEt2 (L2 = 2.2'-bipyridyl(2.2'-bipy); 1.10-phenanthroline (ophen)) (1, 2) with two equivalents of tert-butylisonitrile results in the elimination of the carbonyl group and the displacement of one iodine ligand from the coordination sphere, leading to the new, cationic carbyne complexes [(I)2(t-C4H9NC)2L2W≡CNEt2]+I- (3, 4). The ionic character and composition of 3 and 4 was confirmed by the electrical conductivity of their solutions as well as by elemental analyses, IR, 1H NMR and 13C NMR spectroscopy.
1,3-Digermapropan und 1,3,5-Trigermacyclohexan / 1,3-Digermapropane and 1,3,5-Trigermacyclohexane
Authors: Schmidbaur Hubert , Rott Johann , Reber Gabriele , Müller Gerhard
Published: March 2015

From the copper-catalyzed reaction of germanium powder with dichloromethane at 350 °C a mixture of alkylchlorogermanes is obtained, in which CH3GeCl3, CH2(GeCl3)2 (1) and (Cl2GeCH2)3 (2) are the major products. Treatment of 1 and 2 with LiAlH4 in di-n-butyl or diethylether, resp., affords the hydrides CH2(GeH3)2 (3) and cyclic (H2GeCH2)3 (4), the latter along with the heterocycle H2Ge(CH2GeH2)2 (5). Compounds 3-5 have been identified by analytical and spectroscopic data, and the crystal structure of 4 has been determined by single crystal X-ray diffraction. The compound crystallizes in the orthorhombic space group Pmn21, with two molecules in the unit cell (a = 8.663(1), b = 7.783(1), c = 6.124(1) Å). The molecules, which are in a chair conformation, have crystallographic mirror symmetry with bond angles slightly larger than tetrahedral and Ge-C distances of 1.944(6), 1.953(3) and 1.955(4) Å. The compounds show potential as substrates for plasma-enhanced chemical vapour deposition (PE-CVD) of amorphous germanium carbon alloys (a-Ge, C:H).
Reaktionen von Natriumdimethylbismutid mit α, ω-Dibromalkanen und Halogenomethyl-trimethyl-metallanen (M = Si, Ge, Sn) / Reaction of Sodium-dimethyl-bismuthide with α, ω-Dibromoalkanes and Halogenomethyl-trimethyl-metallanes (M = Si, Ge, Sn)
Authors: Wieber Markus , Rudolph Klemens
Published: March 2015

The bis(dimethylbismuth)alkanes (CH3)2Bi(CH2)nBi(CH3)2 (n = 3, 4, 5) were prepared by reaction of NaBi(CH3)2 in liquid ammonia with dibromoalkanes Br(CH2)„Br (n = 3, 4, 5). Thermolysis of bis(dimethylbismuth)butane and bis(dimethylbismuth)pentane leads to the cyclic compounds 1-methyl-bismacyclopentane and 1-methyl-bismacyclohexane. Reaction of NaBi(CH3)2 with halogenomethyl(trimethyl)metallanes XCH2E(CH3)3 ( E = Si, Ge, Sn; X = Hal) produce compounds of the type (CH3)2BiCH2E(CH3)3.
Tetrakis-pentamethylcyclopentadienyl-cyclotetrastiban (PcpSb)4 : Synthese, Molekül-und Kristallstruktur / Tetrakis-pentamethylcyclopentadienyl-cyclotetrastibane (PcpSb)4 : Synthesis, Molecular and Crystal Structure
Authors: Berlitz Theo F. , Sinning Heike , Lorberth Jörg , Müller Ulrich
Published: March 2015

Reaction of SbCl3 with KPcp (Pep = pentamethylcyclopentadienyl) in etheral solution at -78 °C affords dimeric pentamethylcyclopentadiene and orange-red (PcpSb)4 in high yield. 1H, 13 C NMR, IR, UV and mass spectra are reported. The tetrameric structure was found by a crystal structure determination carried out with X-ray diffraction data collected at -50 °C (928 independent observed reflexions. R = 0.055). Crystal data: tetragonal, space group I41/amd, a = 2400.0(5), c = 781.7(5) pm, Z = 4. The (PcpSb)4 molecules have a non-planar Sb4 ring with Sb -Sb bond lengths of 285.6(1) pm, one η1-Pcp ring is attached to each Sb atom. Contrary to the solid state structure, monomeric molecules are found in benzene and hexane solutions.
Tricyclische β-Lactame, VI. Synthese und Struktur von 5,6,6-Trimethyl-2,3-benzo-4-thia-1-azabicyclo- [3.2.0]heptan-7-on, einem neuen β-Lactamgrundgerüst / Tricyclic β-Lactames, VI. Synthesis and Structure of 5,6,6-Trimethyl-2,3-benzo-4-thia-1-aza-bicyclo[3.2.0]heptane-7-one, a New Basicskeleton of β-Lactames
Authors: Santer Gerhard , Ongania Karl-Hans , Hofer Klaus , Gieren Alfred
Published: March 2015

The title compound 1 was prepared by cyclization of the dihydrobenzthiazole-acetic acid 6 and characterized by X-ray structure analysis.
Synthesis of Quaternary Salts from 4,7-Phenanthroline and Dibromoalkanes
Authors: Singh Shyam K. , Summers Lindsay A. , Hick Larry A.
Published: March 2015

4,7-Phenanthroline, Quaternary Salts, Dibromoalkanes 4,7-Phenanthroline reacts with dibromoalkanes to afford 4-bromoalkyl-4,7-phenanthrolinium bromides. 4-(3-Bromo-propyl)-and 4-(4-bromobutyl)-4,7-phenanthrolinium bromides on heat-ing afford the corresponding 4,4'-(alkanediyl)-bis-4,7-phenanthrolinium diquaternary salts whereas 4-(5-bromopentyl)-and 4-(6-bromohexyl)-4,7-phenanthrolinium bromides give the corresponding bridged diquaternary salts which are the first representatives of new heterocyclic ring systems.
Zur Koordination unterschiedlicher Hauptgruppenmetalle mit einem speziellen, chelatisierenden Silazan / On the Coordination of Different Main Group Metals with a Special, Chelating Silazane
Authors: Veith M. , Goffing F. , Huch V.
Published: March 2015

The cis-isomer of the silazane H2L (1) (L = [NtBu][Me]Si(NtBu)2Si[Me][NtBu]) has been used as a ligand to main group metals. By displacing the hydrogen atoms of 1 the compounds L(MgMe)2 (4), L(MgCl)2 (5) and L(Li)(InMe2) (6) have been obtained. According to the 1H NMR spectra the structures of 4-6 are very similar: a polycyclic, cubane-like Si2N4M2 framework results from the special atomic arrangements and from intramolecular Lewis acid-base interactions between the metals M and the nitrogen atoms. Divalent metals and metal-centered groups can also be incorporated into 1. In the latter case a seco norcubane-like polycycle Si2N4M is produced as confirmed by X-ray structure determinations of LGaMe (8) and LSb+ InCl4
- (11). LInMe (7) and LSn (9) seem to adopt the same tricyclic structure as 8, although the 1H NMR spectra are not consistent with a rigid molecule (low symmetry), but rather with a fluxional behaviour (high symmetry). When 5 is allowed to react with sodium/naphthalene in THF part of the magnesium is reduced and LMg(THF)2 (12) is formed. An X-ray structure determination of 12 reveals the compound to be only bicyclic with the magnesium atom coordinated by two nitrogen and two THF oxygen atoms.
Ein weiteres Silicat-Anion: [Si(NCSe)6]2– / A Further Silicate Anion: [Si(NCSe)6]2–
Authors: Heininger Wolfgang , Polborn Kurt , Nagorsen Günter
Published: March 2015

Reaction of SiCl4 with NMe4NCSe or NEt4NCSe in cold acetonitrile leads to the corresponding crystalline salts of the new hexa-coordinate silicon complex anion [Si(NCSe)6]2- (1 ] ; . Their crystallographic data were determined: [NMe4]2[Si(NCSe)6]: rhombohedral. R3̄. a = 897 pm. a = 84.1°. Z = 1. [NEt4]2[Si(NCSe)6], tetragonal modification (from pure acetonitrile): P42/m, a = 1056 pm. c - 1580 pm. Z = 2. [NEt4]2[Si(NCSe)6]. orthorhombic modification (from acetonitrile containing NEt4Cl): a = 1704 pm. b = 1986 pm. c = 1028 pm. Z = 4. N-bonding of the NCSe groups in [Si(NCSe)6]2 is proved by the X-ray structure analysis of [NMe4]2[Si(NCSe)6] and by IR spectra. The concentration dependence of the molar conductance of an acetonitrile solution of [NMe4]2[Si(NCSe)6] was studied. At low concentrations partial dissociation of the hexa-isoselenocyanatosilicate ion is observed.
The Preparation and Metal Complexing Properties of Isonitrile-Functionalized Polystyrene Resins
Authors: Berry Madeleine , Csorba Janice , Champaneria Ramesh K. , Howell James A. S.
Published: March 2015

Preparation of cross-linked isonitrile-functionalized polystyrene resins of the type ⓟ-C6H5(CH2)nNC (n = 1,2) is described. The polymers extract a variety of normal oxidation state metals from aqueous tetrahydrofuran and anhydrous metal salts and organometallic complexes from tetrahydrofuran and toluene. Structures of the complexes species are assigned on the basis of analyses and infrared spectra.
Flüssigkristalline Kohlenhydratdithioacetale / Liquid Crystalline Carbohydrate Dithioacetals
Authors: Eckert Andreas , Kohne Bernd , Praefcke Klaus
Published: March 2015

S,S-dialkyl acetals of hexanal and numerous aldoses, tripodal in structure, have been synthesized, characterized and investigated by optical microscopy and D.S.C. Most of these geminal dithioacetals show a complicated melting behaviour and are thermotropic liquid crystal-line, exhibiting only one smectic-like phase of identical type. This mesophase is not miscible with the SAd -Phase of other amphiphilic sugar-based liquid crystals. As shown in a homologues series of D-glucose S,S-dialkylacetal derivatives clearing points are rising as function of growing number n of carbon atoms in their S-alkyl chains. With constant n given a similar trend is observed by varying the length of the polar, hydrophilic sugar units. Regarding stereochemistry the dithioderivatives 5 and 12 of the pentose or hexose series, respectively, with a configuration related to that of D-mannose exhibit relatively the most stable mesophase. However, the most stable mesophase of all investigated sugar dithioderivatives is exhibited by the heptose S,S-dialkylacetal 13. Surprisingly, derivative 10 of L-rhamnose (6-desoxy-L-mannose) - the terminal hydroxyl group in the sugar chain of mannose is missing! -showed to be non-mesomorphic, demonstrating that a terminal hydroxyl group of these sugar derivatives seems to be essential for exhibiting a mesophase. On the other hand, as shown with the dithioderivative 9 of 2-desoxy-D-glucose in comparison to the derivative 8e and 12 of D-glucose or D-mannose, respectively, their clearing points seem to be less, although differently effected if an internal hydroxyl group - for instance here at C-2 - has been stripped off.

Melting behaviour as well as thermomesogenic properties of the presented amphiphilic carbo-hydrate liquid crystals in relationship to their molecular structure are discussed in detail.
Notiz über Mono- und Bisaddukte von Diketen an (–)-Menthon / Note on Mono- and Bisadducts of Diketene to (–)-Menthone
Authors: Dehmlow Eckehard V. , Sleegers Arthur
Published: March 2015

1,3-Dioxin-4-ones from Ketones Onium salt and acid catalyzed addition of di-ketene to (-)-menthone gives improved yields of 2 and 3. Excess of diketene leads to diastereomeric mixtures of compounds 4 and 6 from menthone and menthol, respectively.
Di(μ-phosphido)cobalt-und -nickel-Verbindungen mit Trimethylphosphanliganden/ Di(μ-phosphido)cobalt and Nickel Compounds with Trimethylphosphine Ligands
Authors: Klein Hans-Friedrich , Gaß Michael , Zucha Ulf , Eisenmann Brigitte
Published: March 2015

Several fortuitous preparations and high yield rational syntheses for [(Me3P)2M(PMe2)]: (1: M = Co; 2: M = Ni) are described. 1 crystallizes in the space group P1̄ (no. 2); a = 975.6(5). b = 943.6(5), c - 904.2(5) pm. α= 63.8(1)°, β = 79.1(1)°, γ = 72.8(1)°. Mixed metal complexes L2Co(PR2)2NiL2 (L = PMe3; R = Me, Ph) evaded detection giving symmetric products exclusively. An improved synthesis of LiP(C6H5)2·dioxane is also described.
Synthese und Struktur eines ungewöhnlichen Molybdän-Heterocyclus durch Substitution eines Phenylringes in ortho-Stellung/ Synthesis and Structure of an Unusual Molybdenum Heterocycle by Substitution of a Phenyl Ring in ortho-Position
Authors: Scholz Uwe , Noltemeyer Mathias , Roesky Herbert W.
Published: March 2015

The new ligand (Me3Si)2 NC(Ph)NP(Ph)2 N(SiMe3) (1) reacts with MOOCl 4 to yield the green metallacycle 4. 4 was characterized by X-ray diffraction. Crystals of 4 are monoclinic, space group P21/n with a = 1061.2(10). b = 1590.5(10), c = 1737.4(20) pm, β = 104.84(7)° and Z = 4. Mo is coordinated octahedrally by two nitrogens of the bifunctional ligand. by one oxygen and three chlorine atoms. The ligand undergoes cyclization, a bond being formed between N and one phenylic o-position.
[Fe(CO)4C(O)NMe2][C(NMe2)3]; die erste Strukturbestimmung einer Organometallverbindung mit dem Carbeniumion [C(NMe2)3]+/ [Fe(CO)4C(O)NMe2][C(NMe2)3]; the First Structure Determination on an Organometallic Compound with the Carbenium Ion [C(NMe2)3]+
Authors: Boese Roland , Bläser Dieter , Petz Wolfgang
Published: March 2015

The crystal structure of the carbamoyl complex [(CO)4FeC(O)NMe2][C(NMe2)3] (1) is described. It crystallizes in the triclinic space group PI (a = 7.876(3), b = 10.098(3), c = 12.067(5)Å, α = 94.25(3), β = 90.94(3), γ = 97.30(3)°, Z = 2) and consists of independent ions. The cation has a planar CN3 array with sp2 hybridized C and N atoms. The carbamoyl group of the anion occupies an axial position in the trigonal bipyramidal environment of the iron atom.
Element–Element-Bindungen, IV. Molekül-und Kristallstruktur des Tetramethyldiphosphans und -diarsans /Element–Element Bonds, IV. Molecular and Crystal Structure of Tetramethyldiphosphane and -diarsane
Authors: Mündt Otto , Riffel Heinz , Becker Gerd , Simon Arndt
Published: March 2015

The molecular and crystal structures of the isotypic compounds tetramethyldiphosphane 1 and -diarsane 2 have been determined by single crystal X-ray diffraction (monoclinic; C2/m; Z = 2; 1/2: -155/-144 °C\a = 540.6(2)/555.8(2); b = 1131.0(6)/l 136.7(6); c -602.5(2)/612.8(2) pm;β = 97.31(3)/95.24(3)°;P-P 221.2(1)/As-As 242.9(1) pm). In accordance with the crystallographically imposed symmetry 2/m, the molecules adopt antiperiplanar conformation. Their crystal structures are closely related to those of the homologues tetramethyldistibane 3 [1] and -dibismuthane 4 [3]. As found for the latter compounds, the E -E units (E = P, As) are also aligned in linear chains, but the intermolecular E···E contacts (P···P 381/As···As 370 pm) do not allow any extended interaction between molecules, which otherwise would result in thermochromic effects.
Triazaphosphinine – Reaktionen, Zwitterionen, P–B-Austausch/ Triazaphosphinines – Reactions, Zwitter Ions, P – B-Exchange
Authors: Meyer Matthias , Kadel Johannes , Oberhammer Heinz
Published: March 2015

2,2-Dichloro-triazaphosphinine (2) reacts with SbF3 in the molar ratio 3:1 to give the mixed halogenated triazaphosphinine (3). New addition compounds 5 and 6 can be formed in the reaction of the zwitter ion 4 and amines or in the reaction of 2.2-difluoro-triazaphosphinine (1) with KCN. Phosphorus-boron-exchange is observed in the reactions of 4 or 2 with BF3 · OEt2. The new C-B -N-heterocycles 8 and 9 are obtained. The gas-phase structure of 1 has been determined by electron diffraction. The scattering intensities are compatible with a planar ring conformation with C2v symmetry and with equivalent NC bond lengths (PN = 1.579(10) Å, NC = 1.299(7) Å, NPN = 109.2(7)°, PNC - 118.1(9)°, CNC - 119.6(7)° and NCN = 127.5(12)°).
Zur Polymorphie von TbCI3/ Polymorphism of TbCl3
Authors: Gunsilius Harald , Borrmann Horst , Simon Arndt , Urland Werner
Published: March 2015

3 different modifications of TbCl3 were synthesized. TbCl, (UCl3-type), probably in a metastable state, crystallizes in space group P63/m with a = 737.63(2) pm, c = 405.71(2) pm and Z - 2. TbCl3 (PuB3-type) crystallizes in space group Cmcm with a = 384.71(6) pm, b = 1177.37(7) pm. c = 851.77(4) pm and Z = 4. h-TbCl3, the high temperature phase being stable above 790 K. crystallizes in space group P42/mnm with a = 642.51(4) pm, c = 1177.14(18) pm and Z = 4.
Synthese und Kristallstruktur von (Cyclopentadienyl)(dicarbonyl)(1,5-di-/Molyl-pentaazadienido)molybdän, (Cp)Mo(CO)2(tolN5tol)/ Synthesis and Crystal Structure of (Cyclopentadienyl)(dicarbonyl)(1,5-di-p-tolyl-pentaazadienido)molybdenum, (Cp)Mo(CO)2(tolN5tol)
Authors: Beck Johannes
Published: March 2015

(Cp)Mo(CO)2(tolN5tol) is formed in the reaction of (Cp)Mo(CO)3Cl with tolNN(NH)NNtol and NaOH in ethanol. It forms red platelike crystals from THF/hexane which crystallize in the monoclinic space group P21/n with the lattice parameters a = 765.6(2), b = 2372.3(3), c = 1149.4(2) pm, β = 97.06(2)°, Z = 4. The structure consists of monomeric complexes. The pentaazadienido ligand chelates with its nitrogen atoms N1 and N3 the Mo atom of a (Cp)Mo(CO)2 unit. The nitrogen atom N5 is not coordinated to the metal atom. Although asymmetrically bonded, the all trans N5 zig zag chain is planar. The N -N distances in the four membered chelate ring are nearly equal (N1 - N2 = 131.0 and N2 - N3 = 132.6 pm)
meso-Substituierte Porphyrine, 5. Korbporphyrine meso-Substituted Porphyrins, 5. Basket Porphyrins
Authors: Volz Heinrich , Hassler Michael
Published: March 2015

2-Pyrryl-(m-terphenyl)-carbinol and 2-pyrryl-(3,3″,5.5″-tetra-t-butyl-m-terphenyl)-carbinol are cyclized in acidic medium to the corresponding raeso-tetraarylporphyrins. The meso-tetraarylporphyrins are transferred to the iron and manganese complexes. The reactions of the iron porphyrins with OH- are studied and the products of these reactions are characterized.
The Structure and Absolute Configuration of Cyclotirucanenol, a New Triterpene from Euphorbia tirucalli Linn
Authors: Khan Abdul Qasim , Ahmed Zaheer , Kazmi Najam-ul-Hussain , Malik Abdul , Afza Nighat
Published: March 2015

The structure and absolute configuration of “cyclotirucanenol” a new triterpene isolated from Euphorbia tirucalli has been established as 24β-methyl-9β-19-cyclolanost-20-en-3β-ol through chemical and spectroscopic studies including 2D-NMR.
Ceramid-1-phosphoethanolamine aus Myxococcus stipitatus/ Ceramide-1-phosphoethanolamines from Myxococcus stipitatus
Authors: Stein J. , Budzikiewicz H.
Published: March 2015

The structures of six ceramide-1-phosphoethanolamines have been elucidated which differ in the long chain base as well as in the fatty acid component
Notizen: High-field (500 MHz) 1H NMR Spectra of Retinoic Acids and Arotinoids by Two-dimensional Chemical Shift Correlation (2D) Spectroscopy
Authors: Perly Bruno , Pappalardo Giuseppe C. , Klaus Michael , Montoneri Enzo
Published: March 2015

The 1H NMR spectra (in DMSO solution at 300 K) of retinoic acids (cis- and trans-isomers) and new arotinoids were run at 500 MHz and assigned by using homo- and heteronuclear two-dimensional (2D) chemical shift correlation experiments. Spectral analysis was indicating, on the basis of 7 values, that the ring C(l)-C(2)-C(3)-C(4)-C(5)-C(6) adopts, in all compounds, a chair conformation.
Über die Reaktion sekundärer Amine mit Lithiumtetrahydridoaluminat
Authors: Linti Gerald , Nöth Heinrich , Rahm Peter
Published: March 2015

Lithium-tris(diethylamino)hydridoaluminate, Lithium-bis(diisopropylamino)dihydridoaluminate. Lithium(tetramethylpiperidino)trihydridoaluminate, NMR Spectra, X-Ray Reactions of diethylamine, diisopropylamine and 2,2,6,6-tetramethylpiperidine with LiAlH4 in various ethers have been studied. Only two well-defined products result from Et2NH, namely LiAlH(NEt2)- and LiAl(NEt2)4 . If molar ratios of Et2NH:LiAlH4 smaller than 3:1 are employed all compounds of the series LiAlH4-n(NEt2)n (n = 0, 1, 2, 3) are present in solutions of tetra-hydrofuran and diglyme. In diethylether insoluble materials consisting predominantly of lithium diethylaminohydridoaluminates and, presumably, small quantities of Li3AlH6 are also formed. At ambient temperature diisopropylamine reacts slowly with LiAlH4 , and LiAlH2(NiPr2)2 can be isolated as a well-defined substitution product. 2,2,6,6-tetramethylpiperidine (tmpH) replaces only a single hydride from LiAlH4 with formation of LiAlH3 (tmp). The reactions have been monitored by 7Li, 13C and 27Al NMR spectroscopy, and the structure of LiAlH(NEt2)3 has been determined by X-ray analysis. The monoclinic compound contains chains of AlHN3 and LiHN3 tetrahedra linked through common edges.
Darstellungen und Strukturen viergliedriger Metall-Stickstoff-Ringe
Authors: Roesky Herbert W. , Seseke Ulrich , Noltemeyer Mathias , Sheldrick George M.
Published: March 2015

Ph3P=NSiMe3 (1) reacts with InCl3 , SnCl2 and FeCl3 to yield (Ph3P=N)2(InCl2)2 • 2DMF (2a), (Ph3P=N)2Sn2Cl4 • 2 CH3CN (3a) and (Ph3P=N)2 (FeCl2)2 (4). The X-ray single crystal structures of 2a, 3a and 4 are reported. The compounds form four-membered rings consisting of alternating metal and nitrogen atoms. 2a and 4 are symmetrical, but 3a has both a Sn(II)Cl and a Sn(IV)Cl3 group in the four-membered ring.
Molecular and Crystal Structure, and EPR Studies of Tetraphenylarsonium [Bis-(1,3-dithia-2-one-4,5-dithiolato)-nickelate], (AsPh4)[Ni(dmid)2]
Authors: Vicente R. , Ribas J. , Zanchini C. , Gatteschi D. , Legros J.-P. , Faulmann C. , Cassoux P.
Published: March 2015

The crystal structure of (AsPh4)[Ni(dmid)2 (dmid2- = 1,3-dithia-2-one-4,5-dithiolato) has been determined by X-ray diffraction studies: crystals are monoclinic, space group P21/n a = 14.724(2), b = 14.305(5), c = 15.570(3) Å, β = 92.20(1)°, V = 3277 Å3 , ᵨx = 1.63 g cm-3 for Z = 4, final conventional agreement indices R = 0.038 and Rw = 0.049 for 2115 unique, observed reflections and 211 variable parameters. The asymmetric unit contains one (AsPh4)+ cation and one [Ni(dmid)2] anion, both in general positions. The anions are isolated from each other by the bulky cations. The [Ni(dmid)2]- ion deviates strongly from planarity: the dihedral angle between the two Ni(dmid) moieties is 10.7°; one of the dmid ligand is almost planar, while the second one is severely puckered. Polycristalline powder and single crystal EPR spectra have been recorded at room temperature. Only one signal was observed in all crystal orientations. The angular depend-ences of the linewidth and of the g values have been determined, as well as the principal g values and directions. These results have been compared to those previously obtained for the analogue (n-Bu4N)[Ni(dmit)2 ] (drnit2- = 1,3-dithia-2-thione-4,5-dithiolato), and discussed in terms of the localization of the unpaired electron on the ligands. leading to a formal (III) and actual (II) nickel oxidation state.
Addukte von Alkalimetallhexacyanoferraten mit Hexamethylentetramin: Die Kristallstrukturen von Na3[Fe(CN)6] · 2C6H12N4 · 5H20 und K3[Fe(CN)6] · 2C6H12N4 · 4H2O
Authors: Meyer Hans-Jürgen , Pickardt Joachim
Published: March 2015

By diffusion of methanolic solutions of hexamethylenetetramine into aqueous solutions of hexacyanoferrates(III) of sodium and potassium, resp., single crystals of the adducts were ob­tained. Na3[Fe(CN)6] · 2C6H12N4-5H2O, orthorhombic, space group Pca21. Z = 4, a = 14.122(4). b = 14.380(4), c = 14.381(4) Å, 3153 reflections, R = 0.044. K3[Fe(CN)6]•2C6H12N4-4H2O, triclinic, space group P1̄, Z = 4, a = 14.125(4), b = 17.808(4), c =14.116(4) Å, α = 114.14(5), β = 94.91(4), γ = 108.36(5)°. 5550 reflections, R = 0.042. Both structures may be regarded as Elpasolite-Iike arrangements of [Fe(CN)6]3- ions, C6H12N4 molecules and [M2(OH2)x]3+ units (M = Na, K; x = 5, 4), linked together unsymmetrically by M-N contacts of metal ions and nitrogen atoms with mean distances of Na-NHMT = 264 pm. Na-NCYan = 243 pm, K-NHMT = 293 pm and K-Ncyan = 290 pm. Stabilization of the crystal structures is obtained by N---H-O hydrogen bonds of coordination water molecules in three dimensions.
Darstellung und Kristallstruktur von (PhN3)2C6H4[(OH)Ni(PhN 3H)2C6H4]2 · 2THF, einem dimeren Ni(II)-Komplex mit einem überbrückenden Bistriazenido-Liganden
Authors: Hörner Manfredo , Fenner Herton , Hiller Wolfgang , Beck Johannes
Published: March 2015

(PhN3)2C6H4[(OH)Ni(PhN3H)2C6H4]2 · 2THF is obtained by the reaction of [(PhN3)2C6H4]Na2 with aqueous NiCl2. It crystallizes from tetrahydrofuran/hexane in the monoclinic space group P21/n, with a = 1574.6(3), b = 2498.5(2), c = 1629.2(2) pm, β = 93.909(3)°, and Z = 4. The Ni atoms are bridged by the bis(phenyltriazenidyl)benzene group and two hydroxyl groups. Two neutral bis(phenyltriazenyl)benzene groups chelate each Ni atom to complete the distorted co­ordination sphere.
Kristall-und Molekülstruktur von N,N'-Bis(1,3-dimethylbenzo[b]-1,3,2-diazaboroIidin-2-yl)carbodiimid
Authors: Sawitzki Gisela , Einholz Wolfgang , Haubold Wolfgang
Published: March 2015

Crystals of the title compound (2) are monoclinic with a = 905.5(3), b = 593.6(2). c - 3243.5(8) pm, β = 95.63(2)°, Z = 4, space group P21/n. The molecule 2 neither has a C2-symmet-rical allene-type nor a D2d -symmetrical cumulene-type structure, but it has a non-linear B-N = C= N - B arrangement and is nearly planar. The central N = C= N angle has a value of 171.9(3)°, the B - N = C angles are 145.9(2)° and 163.1(3)°.
Die Kristallstrukturen von (1,5-Ditolylpentaazadienido)(triphenylphosphan)gold(I) und 1,5-Ditolyl-3-methylpentaazadien / The Crystal Structures of (1,5-Ditolylpentaazadienido)(triphenylphosphane)gold(I) and 1,5-Ditolyl-3-methylpentaazadien
Authors: Beck Johannes
Published: March 2015

PPh3Au(tolN5tol) is obtained by the reaction of PPh3Au+ClO4
- with Tl(tolN5tol). It crystallizes in the monoclinic space group P21/c with the lattice parameters a = 1548.8(5), b = 1070.7(2), c = 1779.1(3) pm, β = 90.33(2)°, Z = 4. In the monomeric complex the gold atom is nearly linearcoordinated by the phosphorus atom of the PPh3 group and nitrogen atom N3 of the pentaazadienido ligand ( N3 - Au - P 178.4°). tolNN(NCH3)NNtol crystallizes in the orthorhombic space group Pccn with the lattice constants a = 2426.7(9), b = 469.3(2), c = 1195.3(4) pm. The unit cell contains four molecules, located on twofold axes. Due to the isolobality of the CH3 and the PPh3Au group, the two structures are closely related. Both contain the typical planar zig-zag chain of five nitrogen atoms with located double bonds N1-N2 and N4 - N5 (from 119.8 to 126.6 pm) and shortened single bonds N2 - N3 and N3 - N4 (132.7 to 140.0 pm).
Elektronentransfer und Ionenpaar-Bildung, 7 [1, 2] Kontakt-Ionenpaare Schwefel enthaltender Radikalanionen / Electron Transfer and Ion Pairing, 7 [1, 2] Contact Ion Pairs of Sulfur-Containing Radical Anions
Authors: Bock Hans , Hänel Peter , Herrmann H.-F , Dieck Heindirk torn
Published: March 2015

The structurally different radical anions M⊖ of peralkylated 1-sila-2,5-diazacyclopentane-3,4-dithione and of tetrakis(isopropylthio)-p-benzoquinone are generated by reduction with potassium/2.2.2-cryptand under aprotic conditions in THF solution. On addition of Li⊕B(C6H5)4
⊖, both form hitherto elusive sulfur-containing contact ion pairs, which are characterized by their ESR/ENDOR spectra.
Elektronentransfer und Ionenpaar-Bildung, 8 [1] 107,109Ag ENDOR-Kopplungen und Redox-Verhalten des Radikal-Kontaktionenpaares aus Bis(triphenyIphosphino)silber(I)-Kation und 3,5-Di(tert-butyl)-o-benzosemichinon-Anion / Electron Transfer and Ion Pairing, 8 [1] 107'109Ag ENDOR Couplings and Redox Behaviour of the Radical Contact Ion Pair from Bis(triphenylphosphino)silver(I) Cation and 3,5-Di(tert-butyl)-o-benzosemiquinone Anion
Authors: Bock H , Hierholzer B , Jaculi D
Published: March 2015

For the first time, 107,109Ag ENDOR measurements in solution are reported. In addition, the formation of the known paramagnetic contact ion pair [Ag⊕(PR3)2(R2H2C6O2
·⊖] on reduction of 3,5-di(tert-butyl)-o-benzoquinone in THF solution containing soluble silver salts and triphenylphosphine is studied by cyclic voltammetry.
Neuartige basische Liganden für die homogenkatalytische Methanolcarbonylierung, XIX [1] Cobalt-katalysierte Carbonylierung von Methanol zu Essigsäure / Novel Basic Ligands for the Homogeneous Catalytic Carbonylation of Methanol, XIX [1] Cobalt Catalyzed Carbonylation of Methanol to Acetic Acid
Authors: Lindner Ekkehard , Reber Jens-Peter , Wegner Peter
Published: March 2015

The bi- to quadridentate 1,3-dioxolane and 1,4-dioxane phosphane ligands PhnP(CH2C3H5O2)3-n (1, 2). PhP(CH2C4H7O2)2 (3), and [-CH2P(Ph)CH2C4H7O2]2 (4) have been investigated with regard to their efficiency in the carbonylation of methanol to acetic acid using cobalt as a component of the catalyst. While 1, 2 are unstable towards acetic hydrolysis. 3 and 4 lead to methanol conversions of >95%, and selectivities to methyl acetate and acetic acid of 33%, and 60%, respectively.
Phosphorverbindungen ungewöhnlicher Koordination, 31 [1] Cycloaddition von Diazoverbindungen an ein P—Chlor-phosphaalken / Phosphorus Compounds with Unusual Coordination, 31 [1] Cycloaddition of Diazo Compounds onto a P—Chloro-phosphaalkene
Authors: Schnurr Werner , Regitz Manfred
Published: March 2015

Chloro bis(trimethylsilyl)methylene phosphane (4) reacts with the diazo compounds 5, 10, 15 and 20 even at low temperatures with formation of the 3H-1,2,4-diazaphospholes 6,11,16 and 21. The products are unstable and decompose either with elimination of nitrogen to yield 1-chloro phosphiranes (9,14, 19 and 22), or isomerize with aromatization (11 → 13) or transformation into 4,5-dihydro-1,2,4-diazaphospholes (6 → 8, 16 → 18) by trimethylsilyl shifts. Silyl groups attached to ring nitrogen are easily hydrolized (8 → 7,13 → 12, 18 → 17), those attached to ring carbon are cleaved by treatment with potassium fluoride in dimethyl formamide (7 → 23, 12 → 24).
Über die Reaktionen von Phosphoryliden mit homodinuklearen Organometallverbindungen des Molybdän und Wolfram / On the Reaction of Phosphorylides with Homodinuclear Organometallic Compounds of Molybdenum and Tungsten
Authors: Endrich K , Alburquerque P , Korswagen R. P , Ziegler M. L
Published: March 2015

We report first the complete study of the reactions of [CpMo(CO)2]2 (Mo≡Mo) (1, Cp = η5-C5H5) with salt-free phosphorus ylides Ph3P=CHR (2, Ph = C6H5; R = H (2a), CH3 (2b), C3H7 (2c), C6H5 (2d)) and with the Nal-adducts of the ylides Ph3P=CMe2 (Me = CH3), PhMe2P=CH2 and (PhO)3P=CH2. With 2, products of the type Cp(CO)2LMo-MoL(CO)2Cp (7, L = ylide) were obtained, and the salt adducts gave addition compounds of the type Cp(CO)2LMo-MoL(CO)2Cp-2NaI (12, L = ylide). These very reactive products represent novel bisphosphonioalkyl complexes, and were characterized by IR, mass and 1H NMR spectrometry. The reaction of 1 with hexaphenylcarbodiphosphorane, C(PPh3)2, leads to a novel double addition product, Cp2Mo2(CO)4[C(PPh3)2]2 (14). Some reactions of compounds 7, 12 and 14 were also studied; 7d (L = CHPh -PPh3) reacts with NaNH2 yielding ammonia and the disodium salt of the novel dianionic complex [CpMo(CO)2(CPh-PPh3)]2
2- (15); 7a (L = CH2-PPh3) reacts with CH3I forming CpMo(CO)3CH3 and traces of CpMo(CO)2(PPh3)I; all compounds of types 7,12 and 14 react with adsorbents (Silica-gel, Al2O3, etc.); thus chromatography is impossible, even under strict protection from air and humidity. A study of the processes occurring during chromatography under various conditions and the resulting products are also reported and discussed.

[CpW(CO)3]2 (18) reacts with 2a forming also a bisphosphonioalkyl complex [CpW(CO)2L]2(L = CH2=PPh3); in this case, the ylide substitutes two carbonyl groups in 18. The compounds [Cp*M(CO)2]2 (M≡M) (Cp* = C5Me5 ; M = Cr, W) apparently do not react with phosphorous ylides; the corresponding Mo compound, [Cp*Mo(CO)2]2 , does react, but only the new mono-nuclear complex Cp*Mo(CO)2(PPh3)Cl (22) could be isolated.
Darstellung und Schwingungsspektren von Alkyl-und Rhodanohydrohexaboraten / Preparation and Vibrational Spectra of Alkyl and Rhodano Hydrohexaborates
Authors: Heinrich A , Preetz W
Published: March 2015

Treatment of B6H6
2- with iodoalkanes and (SCN)2 in organic solvents affords the monosubstituted protonated hexaborates RB6H6
-, R = CH3, C2H5< C3H7, C4H9, C8H17 and SCN, respectively. The acidity constants of these weak Brönsted acids range for the alkylated species from 8.8 to 9.6, and for R = SCN the pka value is ~5. From basic solutions the salts Cs2RB6H5 can be precipitated, which show band patterns in the IR and Raman spectra typical for monosubstituted hydrohexaborates. The protonated compounds RB6H6
- are distinguished from the corresponding Brönsted bases RB6H5
2- by a high frequency shift of the BH stretching vibrations in the order of 100 cm-1. For Cs2(SCN)B6H5, S coordination of SCN- is supposed because of the high frequency of νCN: 2144 cm-1.
Untersuchungen zur Chemie von Isoindolen und Isoindoleninen, XXXII [1] Elektrophile Substitutionsreaktionen von 2-Aryl-2H-isoindolen mit Trifluoressigsäureanhydrid / Studies on the Chemistry of Isoindoles and Isoindolenines, XXXII [1] Electrophilic Substitution Reactions of 2-Aryl-2H-isoindoles with Trifluoroacetic Anhydride
Authors: Kreher Richard P , Feldhoff Udo , Jelitto Frank
Published: March 2015

The reaction of 2-aryl-2H-isoindoles with trifluoroacetic anhydride in pyridine leads to the formation of the corresponding 1-trifluoroacetyl-2-aryl-2H-isoindoles with acceptable yields. 1-Alkylthio-2-aryl-2H-isoindoles can be generated from 3-alkylthio-2-aryl-1 H-isoindolium-tri-fluoromethanesulfonates with pyridine and acylated in the same manner. Protonation occurs at 1-position and yields isolable 1H-isoindolium salts.
Carnivora: The Primary Structure of the Major and Minor Hemoglobin Components of Adult North Persian Leopard (Panthera pardus sexicolor)
Authors: Ahmed Aftab , Jahan Meeno , Braunitzer Gerhard , Göltenboth Reinhard
Published: March 2015

The complete primary structure of the two hemoglobin components of the adult North Persian Leopard are presented. The major component Hb-I accounts for 80-90% and the minor component Hb-II accounts for 20-10% of the total hemoglobin. Reversed phase HPLC was used for the separation of the polypeptide chains. The amino acid sequences were established by automated Edman degradation of the globin chains and of the tryptic peptides in liquid-and gas-phase sequenators. The sequences are aligned with those of human Hb-A. Our result shows that the hemoglobins of North Persian Leopard and Jaguar are identical in amino acid sequence.
Nitriles in Heterocyclic Synthesis: New Approaches for Synthesis of Some Pyridine Derivatives
Authors: Ibrahim N. S , Mohareb R. M , Shams H. Z
Published: March 2015

A variety of pyridines was prepared from reaction of N-benzylidenecyanoethanoic hydrazide (2) with malononitrile, benzoylacetonitrile, cyanoacetamide and cinnamonitrile derivatives. The reactivity of 2 towards a variety of ketones was studied.
Notizen: Amphiphilic Carbohydrate-based Mesogens, 3 [1] D-MannitoI-1-O-n-Alkyl Ethers with Hydroxy and 1-O—D-Mannityl End-Groups: Novel Double-Headed Thermotropic Liquid Crystals
Authors: Dahlhoff Wilhelm Volker
Published: March 2015

Mesogenic 1,16-di-(1 -O - D-mannityl)-hexadeca-ne (8), 1,22-di-(1-O-D-mannityl)-docosane (9), 1-(1-O - D-mannityl)-hexadecane-16-ol (10) and 1-(1-0 - D-mannityl)-docosane-22-ol (11) are prepared from the respective α,ω-diols by glycosylation followed by glycoside reduction and deprotection.
Perchlorierte Poly-arylen-Derivate / Perchlorinated Poly-arylene Derivatives
Authors: Fritz Heinz P. , Trübenbach Thomas
Published: March 2015

Poly-arylenes, which can be doped to electronic conduction, can be perchlorinated by SCl2 in CCl4 in the presence of iron metal. These polymers can be modified by introduction of CN or PPh2 groups, which can function as ligating groups for metal species.
Speicherung des labilen Silaethens Me2Si=C(SiMe3)2 mit Benzophenon [1] / Storing of the Labile Silaethene Me2Si = C(SiMe3)2 with Benzophenone [1]
Authors: Wiberg Nils , Preiner Gerhard , Schurz Klaus , Fischer Gerd
Published: March 2015

Benzophenone Ph2C=O is able to “store” the silaethene Me2Si=C(SiMe3)2 (1). produced from Me2SiX-CLi(SiMe3)2 (X = F. Br, Ph2PO4), under formation of a [2+4] cycloadduct (2b). At about 100 °C, 2b by way of 1 transfers into the [2+2] cycloadduct of 1 and Ph2C=O (3b), which in the course of transformation decomposes visibly (in the absence of Me3SiCl) or only by traces (in the presence of Me3SiCl) to secondary products. In the presence of ROH (R = H. Me. tBu. MeCO) or PhN = NSiMe3 or RN3 (R = tBu. Me3Si) or 2,3-dimethylbutadiene (dmb) about 100 °C 2b and 3b form by way of 1 insertion products of 1 into the OH bond of ROH or a [2+2] cycloadduct of 1 and PhN = NSiMe3 or [2 + 3] cycloadducts of 1 and RN3 or a [2+4] cycloadduct and an ene reaction product of 1 and dmb. The rate constants/half lives of the first order transformation of 2b into 3b or of the first order decomposition of 2b or of 3b in the presence of reactiv traps for 1 (ROH. Me3SiN3; benzene as solvent) are in the order of 0.3 × 10-4 s-1/τ1/2 = 7 h (2b→3b; 90 °C) 3 3×10-4 s-1/τ1/2 = 3/4 h (2b + traps; 90 °C), 0.4 × 10-4 s-1/τ1/2 = 5 h (3b + traps. 110 °C).
Tetraphospholan-Bildung via Phosphaalken durch LiSnPh3-katalysierte PhP-Übertragung / Formation of a Tetraphospholane via Phosphaalkene by LiSnPh3-Catalyzed Transfer of PhP Units
Authors: Zirzow Karl-Heinz , Schmidpeter Alfred
Published: March 2015

Lithium triphenylsilyl-phenylphosphide (3), X = SiPh3 , reacts with ketones to give tetraphenyl-phospholanes (6). In an initial step a phosphaalkene 5 is formed, which then adds three more phenylphosphinidene units. This second step can be performed independently, and the PhP units can be furnished by pentaphenylcyclopentaphosphane (1) if the reaction is catalyzed by lithium triphenylstannide (2), X = SnPh3.
Silberdiammin-disilber-hexacyanometallate(III): Kantenverknüpfte Doppeltetraeder-Einheiten Ag2N6 in den unterschiedlichen Strukturen von Eisen- und Cobaltkomplex / Silverdiammine Disilver Hexacyanometallates(III): Edge-Sharing Tetrahedra Ag2N6 in the Different Structures of Iron and Cobalt Complex
Authors: Ziegler B. , Seitz K. , Babel D.
Published: March 2015

The crystal structures of the monoclinic compounds Ag(NH3)2Ag2Fe(CN)6 (a = 948.2, b = 1235.5, c = 1246.8 pm, β = 94.98°. Z = 4. space group Cc) and Ag(NH3)2Ag2Co(CN)6 (a = 772.1, b = 1347.9, c = 1405.2 pm, β = 101.25°, Z = 4, C2/c) have been determined by x-ray methods from single crystals. Using 1947 and 2739 reflections, resp.. R factors of about 5% were reached. Both compounds are similar in containing approximately linear Ag(NH3)2
+ dumb-bells (Ag-N = 216 pm) and dimeric Ag2N6 units. The latter consist of distorted edge-sharing tetrahedra (average Ag-N = 229 and 231 pm, resp.), the cavities of which are provided by the nitrogen ends of six surrounding M(CN)6
3- octahedra (Fe -C =195 pm, Co -C = 189 pm, C - N = 115 and 114 pm, resp.). In the iron complex, which is elpasolite-related, the central Ag2N2 ring is planar (Ag-Ag = 327.0 pm). By contrast the unit is folded (Ag-Ag = 307.8 pm, dihedral angle 126° between AgN2 triangles) in the cobalt complex, which has a different structure as discussed in detail
Molybdännitridtrichlorid-2,3,3-trichloracrylnitril, [MoNCI3 · NC-C2Cl3]2 Synthese, IR-Spektrum und Kristallstruktur / Molybdenumnitridetrichloride-2,3,3-trichloroacrylnitrile, [MoNCl3 · NC—C2Cl3]2 Synthesis, IR Spectrum, and Crystal Structure
Authors: Khabou Abderraouf , Dehnicke Kurt
Published: March 2015

[MONCl3 · NC - C2Cl3]2 has been prepared by the reaction of MONCl3 with trichloromethyl isocyanidedichloride, CCl3NCCl2 , in CH2Cl2 suspension. The compound forms redbrown. mois-ture sensitive crystals, which were characterized by their IR spectrum as well as by a crystal structure determination (2482 independent observed reflexions, R = 0.048). Crystal data (-70 °C): Space group P21/c, Z = 2, a = 674.2(2); b = 2128.2(11); c = 786.0(4) pm: β = 102.81(3)°. [MONCl3 • NC-C2Cl3]2 forms centrosymmetric dimeric molecules via chloro bridges with Mo-Cl bond lengths of 240.7 and 276.0 pm. The longer MoCl bond of the MOCl2MO ring is caused by the trans influence of the nitride ligand; the MoN bond length of 167 pm corresponds with a triple bond. The 2,3,3-trichloroacrylnitrile ligand is bonded by its nitrogen atom with a bond length of Mo -N = 216 pm; the Mo-N≡C-C sequence is almost linear with a remarkable short C-C bond of 143.0 pm.
Amidinatokomplexe von Bor, Aluminium, Gallium, Indium und Zinn Die Kristallstrukturen von Ph-C(NSiMe3)2AICI2 und Ph-C(NSiMe3)2SnCl3 / Amidinato Complexes of Boron, Aluminium, Gallium, Indium, and Tin The Crystal Structures of Ph-C(NSiMe3)2AlCl2 and Ph-C(NSiMe3)2SnCl3
Authors: Ergezinger Christina , Weller Frank , Dehnicke Kurt
Published: March 2015

The trichlorides of aluminium, gallium, and indium, as well as boron tribromide and tin tetra-chloride react with N,N,N'-tris(trimethylsilyl)benzamidine to form the monomeric N.N'-bis-(trimethylsilyl)benzamidinato complexes Ph-C(NSiMe3)2MX2(M = B, Al. Ga, In; X = Cl, Br) and Ph -C(NSiMe3)2SnCl3 , respectively. All compounds have been characterized by their IR spectra, two of them by X-ray diffraction studies.

Ph - C(NSiMei)2AlCl2 : Space group C2/c, Z = 4, 1152 independent observed reflexions, R = 0.052. Lattice dimensions (19 °C): a = 1558.6(1), b = 1116.6(1), c = 1307.0(1) pm, β = 115.17(1)°. The compound forms monomeric molecules, in which the aluminium atom is tetra-hedrally coordinated by two chlorine atoms and by the two nitrogen atoms of the benzamidinato chelate. Bond length A1N = 188.2 pm.

Ph - C(NSiMe3)2SnCU: Space group P1̄, Z = 2, 3293 independent observed reflexions, R = 0.034. Lattice dimensions (19 °C): a = 980.1(1), b = 1025.9(1), c = 1230.5(2) pm. a = 68.40(1)°, β = 87.71(1)°, y - 68.92(1)°. The compound forms monomeric molecules, in which the tin atom is five-coordinated by three chlorine atoms and by the two nitrogen atoms of the benzamidinato chelate. Bond lengths SnN = 213.5 and 215.2 pm.
Metallocene o-Phenylenebis(phenylphosphido) Chelates of Molybdenum and Tungsten / Metallocene o-Phenylenebis(phenylphosphido) Chelates of Molybdenum and Tungsten
Authors: Köpf Hartmut , Richtering Verena
Published: March 2015

The reaction of the metallocene dichlorides Cp2MCl2 (Cp = η5-C5H5; M = Mo, W) with equimolar amounts of dilithium-o-phenylenebis(phenylphosphide) 1,2-(LiPPh)2C6H4 yields the five-membered chelate complexes Cp2M[1,2-(PPh)2C6H4] (M = Mo. 1; W, 2). Compounds 1 and 2 are characterized by IR, NMR and mass spectra
Struktur und Reaktivität von isoanellierten heterocyclischen Systemen mit 4nπ- und (4n+2)π-Elektronen, XVII [1] Diels-Aider- und Michael-Additionsreaktionen von 3-Alkoxy-2,4-dihydropyrrolo[3,4-b]indolen mit Ethindicarbonsäuredialkylestern / Structure and Reactivity of Isoannelated Heterocyclic Systems with 4nπ- and (4n+2)π-Electrons, XVII [1] Diels-Alder and Michael Addition Reactions of 3-Alkoxy-2,4-dihydropyrrolo[3,4-b]indoles with Dialkyl Acetylenedicarboxylates
Authors: Dyker Gerald , Kreher Richard P.
Published: March 2015

The reactions of 2-rm-butyl-3-methoxy-4-methyl-2,4-dihydropyrrolo[3,4-b]indole (3) with dialkyl acetylenedicarboxylates are decisively influenced by the solvent. In the presence of alcohols as protic and polar solvents Michael addition is prefered, while in aprotic and less polar solvents like ether the Diels-Alder reaction is favoured. Based on stereospecific hydrolysis and isotopic labeling dipolar intermediates are discussed. The results are of current interest for mechanistic and theoretical reasons
Reaktionsbeteiligung von Phosphonester-Nachbargruppen bei Amindehydrierungen / Participation of Phosphonate Neighbour Groups with Dehydrogenations of Amines
Authors: Möhrle Hans , Vetter Wolfgang
Published: March 2015

Aminomethanephosphonate. Mercury EDTA Dehydrogenation. Lactam. Formamide, Aminoalkylation Aminophosphonates 1-5 are dehydrogenated with mercury EDTA to the corresponding lactams 6-9 and surprisingly to the formamide derivative 10, The different rate of ester hydrolysis of these acylamine compounds, the steric requirements and the reaction mechanisms are dis-cussed.
Synthese und Kristallstruktur von tetramerem N,N'-Diphenylformamidinato-gold(I), [Au(PhNCH NPh)]4/Synthesis and Structure of Tetrameric N,N'-Diphenylformamidinato Gold(I), [Au(PhNCHNPh)]4
Authors: Hartmann Edmund , Strähle Joachim
Published: March 2015

Abstract N.N'-Diphenylformamidinato gold(I) (1) is obtained from Na(PhNCH NPh) and Aul in liquid ammonia. It can be recrystallized from toluene/n-heptane to form colorless monoclinic crystals, the space group C 2/c, with the lattice constants a = 1781.7(7), b = 1159.0(5), c = 2518.7(8) pm, β = 99.06(3)°. 1 is tetrameric in solution and in the solid state. In the tetrameric complex with the symmetry C2 the four Au atoms form a planar rhombus with Au -Au distances between 295,7 and 322.7 pm. The amidinato ligands are arranged alternatively above and below the Au4-rhombus and function as bridging ligands for neighbouring Au atoms, which thereby reach a linear coordination with distances A u -N between 200.0 and 202.4 pm.
Photoionisationsmassenspektren von MethyI(trifluormethyl)sulfan CH3SCF3 [1]/Photoionization Mass Spectra of Methyl(trifluoromethyl)sulfan CH3SCF3 [1]
Authors: Hagenow G. , Jochims H.-W. , Sawatzki J. , Minkwitz R. , Baumgärtel H.
Published: March 2015

The ionization potential of CH3SCF3 and the appearance potentials of fragment ions have been measured in the photon energy range 9 -19 eV using synchrotron, radiation. From these results thermochemical data of CH3SCF3, CH3SCF3
+ and fragment ions have been evaluated.
Dithiocarbimates from Sulfonamides, Part 1: Preparation and X-Ray Crystal Structures of K2[S2C = N—SO2—C6H5] · 2H2O and K2[S2C = N—SO2—C6H4—Cl] · 2H2O
Authors: Hummel Hans-Ulrich , Korn Uwe
Published: March 2015

Dithiocarbimates. Sulfonamides, X-Ray. Sulfones By reaction of the sulfonamides C6H5-SO2-NH2 and p-Cl-C6H4-SO2-NH2 with CS2 in the presence of bases the corresponding dithiocarbimates have been obtained in form of their potassium salts and characterized by means of X-ray structural analysis. Both compounds crystallize in the space group P21/a with a = 29.778(3), b - 6.202(1). c = 7.169(1) Å and β = 90.33(2)° for K2[S2C = N-SO2-C6H5] · 2H2O and a = 31.517(3). b = 7.189(1), c -6.196(1) Å and β = 90.10(1)° for the Cl-substituted species, respectively. A relation between both crystal structures becomes obvious when for K2[S2C = N-SO2-C6H4-Cl] · 2H2O the first space group setting is choosen; i.e. P 1 1 21/a. The dithiocarbimates are built up of two planar moieties. One plane contains the S2C = N-SO framework of each anion while a second plane consists of the S-C6H5 group and the S-C6H4-Cl group, respectively. The two planes are oriented nearly perpendicular to each other and give rise to conjugation involving the SO2 groups in the different systems.