bluuebunny/crossref_metadata_2025 huggingface dataset:
Titan- und Vanadiumkomplexe mit 4-[1-(N′-Benzoylhydrazino)-l-phenylmethyliden]- 3-methyl-1-phenyl-pyrazol-5-on. Röntgenkristallstruktur von 4-[1-(N′-Benzoylhydrazino)-1-phenyl-methyliden]-3-methyl-1-phenyl- pyrazol-5-on / Titanium- and Vanadium Complexes of 4-[1-(N′-Benzoylhydrazino)-1-phenylmethylidene]-3-methyl-1-phenyl-pyrazol-5-one. Structure of 4-[1-(N′-Benzoylhydrazino)-1-phenyl-methylidene]-3-methyl-1-phenyl-pyrazol-5-one
Authors: Kraudelt Heide , Schilde Uwe , Hefele Heike , Ludwig Eberhard , Ludwig Erhard
Published: February 2015

By reaction of 1-phenyl-3-methyl-4-benzoyl-pyrazol-5-one with benzoylhydrazine the tridentate diacidic ligand 4-[1-(N′-benzoylhydrazino)-1-phenyl-m ethylidene]-3-m ethyl-lphenyl-1-pyrazol-5-one (H2L) is formed which gives complexes ML2 with tetravalent titanium and vanadium ions. The ligand and its complexes were characterized by mass spectroscopy. The vanadium(IV) complex can be oxidised and reduced electrochemicallv. The chemical bonding in the titanium(IV) complex and in the ligand was studied by IR and 13C NMR spectroscopy.

The molecular structure of 4-[1-(N′-benzoylhydrazino)-1-phenyl-methylidenel-3-m ethyl-lphenyl- pyrazol-5-one was determined by X-ray analysis. Crystal data: a = 9.159(3) Å, b = 11.014(4) Å, c = 11.136(5) Å, a = 90.11 (2)°, β = 101.84(3)°, γ = 113.01 (2)°; space group P1̄, Z = 2.
Spektroskopische und strukturelle Aspekte der Protonierung von Tetraaza[14]annulen-Dianionen / Spectroscopic and Structural Aspects of the Protonation of Tetraaza[14]annulene Dianions
Authors: Schumann H. , Neumann B. , Stammler H.- G.
Published: February 2015

The effects of increasing protonation upon two [ 14]annulene dianions prepared by reaction of LiCH3 with 5,14-dihydro-6,8,15,17-tetramethyldibenzo[b,i][l,4,8,l l]tetraazacyclotetradecine (IIIb) and 5,14-dihydro-6,17-dimethyl-8,15-diphenyldibenzo[b,i][l,4,8,l 1 ]tetraazacyclotetradecine (IIIc) have been studied by 1H, 13C NMR and UV-VIS spectroscopy in solution. The crystal structures of the diprotonated macrocycle IIIb x 2 HPF6 (lIb) and of the neutral macrocycle IIIc have been determined by X-ray diffraction. For lIb, the crystal system is monoclinic with a space group of P21/n: a = 12.019(3), b = 13.864(6), c = 33.547(9) Å, β = 99.82(2)°, Z = 8 . The final R factor is 0.083 for 5520 observed reflections (745 variables). For IIIc, the crystal system is triclinic with a space group of P1̄: a = 9.923(8), b = 11.633(9), c = 14.318(12) Å, ct = 110.50(6)°, β = 98.86(7)°, 7 = 103.12(6)°, Z = 2. The final R factor is 0.081 for 2174 observed reflections and 191 variables. Comparison of these structural data together with those obtained from the literature for the deprotonated macrocycle IVb and a wide variety of substituted [ 14]annule derivatives allows for the first time a discussion of protonation effects upon the highly π-conjugated pentadiimidato moiety. Additional information is derived from NMR and UV-VIS data.
N-Functionalization of the Tetrahedrane Fe2(CO)6(μ-SNH)
Authors: Herberhold Max , Bertholdt Uwe , Milius Wolfgang , Wrackmeyer Bernd
Published: February 2015

The azadiferrathia tetrahedrane, Fe2(CO)6(μ-SNH) (1), was deprotonated to give the anion [Fe2(CO)6(μ-SN)]− (2) which reacts with halides of phosphorus, arsenic, silicon, germanium, tin and boron by formation of element-nitrosen bonds. The new compounds were characterized by their IR. NMR (1H ,11B, 13C, 15N, 29Si, 31P, 119Sn)and mass spectra. The molecular structure of [Fe2(CO)6(μ-SN-SiMe2CH2-)]2 (11) was determined by X-ray structure analysis (space group P1̄; triclinic; a = 799.8(2), b = 958.5(2), c = 1035.7(2) pm, a = 86.30(2)°, α = 81.27(2)°, β = 69.90(2)°).
Polysulfonylamine, LXXVI [1] Zwei supramolekulare Isomere im gleichen Kristall: Darstellung und Struktur des monomeren 18-Krone-6-Komplexes (CH2CH2O)6·2 MeN(SO2Me)(SO2Ph) / Polysulfonylamines, LXXVI [1] Occurrence of Two Supramolecular Isomers in One Crystal: Synthesis and Structure of the Monomeric 18-Crown-6 Complex (CH2CH2O)6 • 2 MeN(SO2Me) (SO2Ph)
Authors: Henschel Dagmar , Hiemisch Oliver , Blaschette Armand , Jones Peter G.
Published: February 2015

The title complex, obtained by co-crystallization of its molecular components from methanol, was characterized by low-temperature X-ray diffraction. The crystal structure (triclinic, space group P1̄, Z = 2) consists of two monomeric and crystallographically centrosymmetric formula units A and B which may be classified as supramolecular stereo- and/or linkage isomers. In both units, the receptor rings adopt the frequently observed D3d pseudosymmetry, and the symmetry-related substrate molecules are situated above and below the polyether rings. The isomerism of the supermolecules arises from markedly different confomations of their substrate components. In B, the methyl groups display a transoid orientation (torsional angle for C - N - S - C : 135.5°) and the N-methyldisulfonylamine is solely attached by three S - C - H ··· O interactions to a set of three alternating crown oxygen atoms. In isomer A, the C -N - S - Cmethyl sequence is cisoid (torsional angle: 83.1°) and the substrate is connected to the crown ether by three S - C - H ··· O bonds and an additional N - C - H ··· O interaction. The H ··· O distances and C -H ··· O angles of the seven independent hydrogen bonds lie within the intervals 230-260 pm and 140-180°, respectively. A supermolecule involving MeN (SO2Ph)2 and 18-crown-6 could not be isolated, whereas the binary complex (CH2CH2O)6•2 MeN(SO2F)2 is readily obtained by co-crystallization of the components. The latter complex showed severe disorder of the N(SO2F)2 moieties and its structure could not be refined satisfactorily.
Combined Solid Phase and Solution Synthesis of the Fully Protected Segment 74-99 of HIV 1-Protease with the Application of a New Trityl-Linker
Authors: Henkel Bernd , Zhang Lianshan , Goldammer Carsten , Bayer Ernst
Published: February 2015

A new trityl-linker for the strategy of combined solid phase and solution synthesis has been used for the synthesis of the fully protected segment 74-99 of HIV 1-protease. The fully protected fragments 74-81, 82-99 and 90-99 have been synthesized on the polystyrenepolyethylenglykol resin TentaGel, split off with dilute acetic acid and assembled in solution without loss of side-chain protecting groups. After protection of the C-terminus of the fragment 90-99, the second fragment was coupled with TBTU/NMM. The couplings were monitored by IS-MS and HPLC. Racemization was checked by chiral gas-chromatography on a Chirasil-Val capillary.
Re-functionalization of 9-Substituted Isocolchicides via Nucleophilic Tele-Substitution. A General Synthesis of 11-Alkyl(Aryl)thioisocolchicides
Authors: Cavazza Marino , Pietra Francesco
Published: February 2015

9-Substituted isocolchicides in methanol or dimethyl sulfoxide undergo ipso-substitution by sodium thiolates in mixture with the corresponding thiols, giving 9-alkyl(aryl)thio-substituted isocolchicides which are prone to in situ tele-substitution affording 11-alkyl(aryl)thio functionalized isocolchicides. Such C-11 activation by dicoordinated sulfur is used here for a general synthesis of 1 l-alkyl(aryl)thioisocolchicides.
Zur Kristallchemie ungeladener Phosphazen-Basen, II [1] Strukturen der wasserfreien Form und zweier Hydrate des Diphosphazens (Me2N)3P=N-(Me2N)2P=NH / Crystal Chemistry of Uncharged Phosphazene Bases, II [ 1] Structures o f the Anhydrous Form and Two Hydrates of the Diphosphazene (Me2N)3P =N-(Me2N)2P=NH
Authors: Hartmann Frank , Mootz Dietrich , Hasenfratz Christian , Schwesinger Reinhard
Published: February 2015

The uncharged, very strong diphosphazene base (Me2N)3P=N-(Me2N)2P=NH (for short P2) and two hydrates have been characterized by crystal structure analysis. The diphosphazene. m. p. 23°C, is triclinic with space group P1̅ and Z = 2 formula units per unit cell of dimensions a = 7.595, b = 7.972, c = 14.642 Å, a = 100.19°, β = 96.15° and 7 = 100.79° at -150°C. A monohydrate, P2·H2O, m. p. 24°C, is monoclinic with P2|/c. Z = 4, a = 11.778, b = 15.415, c = 10.190 Å, and β = 93.46° at -100°C. Another hydrate, Pr 2.25 H2O. m.p. 14°C, is also monoclinic with P21/c, Z = 8, a = 10.348, b = 25.476, c = 15.791 A, and ,3 = 105.70° at -100°C. In the structure of the anhydrous diphosphazene there are no distinct intermolecular interactions. In the hydrate P2·H2O, a centrosymmetric dimer of the formula unit is formed by hydrogen bonds O-H···N arranged in a centrosymmetric four-membered ring. In the hydrate P2·2.25 H2O. hydrogen bonding O-H···O and O-H···N generates an aggregate of five fourmembered rings, alternating with a single water molecule in an unlimited chain. In spite of the high basicity of the diphosphazene, its hydrate structures are not ionic but clearly molecular.
Darstellung und Kristallstruktur von [SCI3][HM0OCl4] / Preparation and Crystal Structure of [SCl3][MoOCl4]
Authors: Beck J. , Hengstmann M.
Published: February 2015

The reaction of sulfur with MoOCI4 in the presence of a large excess of ICl3 in a sealed evacuated ampoule at 100 °C yields [SCl3][MoOCl4] in the form of yellow-brown, moisture sensitive crystals. The crystal structure determination (monoclinic space group P21/n; lattice constants a - 971,1(1) pm, b = 926,9(1) pm. c = 1220,6(1) pm, β = 112,68(1)°, Z = 4) shows that the title compound consists of square pyramidal [MoOCl4]- anions and trigonal pyramidal [SCl3]+ cations. Two [MoOCl4]- anions are linked by asymmetric chlorine bridges and form centrosymmetric dimers [Mo2O2CI8]2- with the oxygen atoms located in the trans positions of the chlorine bridges. Two trigonal pyramidal [SCl3]+ cations are connected by secondary sulfur chlorine interactions with the [Mo2O2CI8]2- anion to form centrosymmetric dimers ([SCl3[MoOCl4])2. The coordination sphere for the sulfur atom is a strongly distorted octahedron with three S-Cl bonds of 199 pm and three weak S-Cl contacts of 304 pm in average length.
Bis[tris(trimethylsilyl)methylzink]tri/sopropyIsilylphosphandiid,ein geminal bis(alkylzink)substituiertes Phosphan / Bis[tris(trimethylsilyl)methylzinc]triisopropylsilylphosphandiide, a Geminally Bis(alkylzinc) Substituted Phosphane
Authors: Westerhausen Matthias , Wieneke Michael , Doderer Kai , Schwarz Wolfgang
Published: February 2015

The reaction of tris(trimethylsilyl)methylzinc chloride with lithium triisopropylsilylphosphanide yields triisopropylsilylphosphane and bis[tris(trimethylsilyl)methylzinc]triisopropyIsilyl-phosphandiide 1. This compound is monomeric in solution as well as in the crystalline state (triklinic, space group P1̅, a = 1184,79(9),b= 1376,48(9), c - 1624,60(14) pm, α =91,909(6)°, β = 107,947(6)°, γ = 113,430(5)°, Z = 2). The Zn-P-distances of 223 pm are very short due to the small coordination numbers of the phosphorus and zinc atoms.
Synthese und Kristallstruktur der (p-Brombenzyl)triphenylphosphonium-bromide: [(p-Br-C6H4-CH2)P(C6H5)3]+B-;[(p-Br-C6H4-CH2)P(C6H5)3]+Br2
- und [(p-Br-C6H4-CH2)P(C6H5)3]+Br3
-/ Synthesis and Crystal Structures of (p-Bromobenzyl)triphenylphosphonium Bromides, [(p-Br-C6H4-CH2)P(C6H5)3]+Br-;[(p-Br-C6H4-CH2)P(C6H5)3]+Br- and [(p-Br-C6H4-CH2)P(C6H5)3]+Br3-
Authors: Vogt H. , Wulff-Molder D. , Meisel M.
Published: February 2015

(p-Bromobenzyl)triphenylphosphonium Bromide,

[(p-Br-C6H4-CH2)P(C6H5)3]+Br- · (CH2Cl2)2.5 (1) has been prepared by the reaction of triphenylphosphine with p-bromobenzylbromide and its structure determined (triclinic, space group P1̅, Z = 2, a = 1198.03(12), b = 1245.80(11), c = 1258.42(12)pm, a = 100.170(8), β = 103.543(9), γ = 1 18.158(7)°. The compound exists as Br- anions and [(p-Br-C6H4- CH2)P(C2H5)3]+ cations, with weak interactions between the chlorine atoms of the CH2Cl2 molecules and the bromine bonded in the cation.

[p-Br-C6H4-CH2)P(C6H5)3]Br2 (2) and [(p-Br-C6H4-CH2)P(C6H5)3]Br3·(CH2Cl2)1.5 (3) have been obtained by reactions of the corresponding amounts of bromine with 1 in methylenechloride solution. The yellow-red crystals of 2 are orthorhombic, space group Pccn, Z = 8, a = 2060.8(3), b = 1223.6(4), c = 1860.8(3) pm. Compound 2 exists as [p-Br-C6H4-CH2)P(C6HO5)3]+ cations and linear Br2-
4 units with a bromide-bromine distance of 297.3(4) pm. The red crystals of (3) are triclinic, space group P1̅, Z = 2, a = 1 171.16(7), b = 1260.97(8), c = 1270.35(7)pm, α = 65.510(5), β = 75.811(5), γ = 62.320(5)°, and contain [(p-Br-C6H4-CH2)P(C6H5)3]+ cations and linear, slightly asymmetrical Br-
3 anions. In all cases the cation has a slightly irregular tetrahedral geometry around the P atom.
Spezielle Alkylammoniumhexachlorometallate, III [1] Synthese und Kristallstruktur von Tris(guanidinium)- hexachlororhodat(III)-monohydrat, [C(NH2)3]3 [RhCl6] · H2O / Alkylammonium Hexachlorometallates, III [1] Synthesis, and Crystal Structure of Tris(guanidinium) Hexachlororhodate(III) Monohydrate, [C(NH2)3]3[RhCl6] · H2O
Authors: Frank Walter , Reiß Guido J.
Published: February 2015

Tris(guanidinium) hexachlororhodate(III) monohydrate, [C(NH2)3]3[RhCl6] · H2O (1 ) has been obtained by the reaction of rhodium(III) chloride with guanidine hydrochloride in hydrochloric acid solution. 1 crystallizes in the triclinic space group P1̅ (a = 7.6013(9) Å, b = 8.6912(10) Å, c = 15.956(2) Å, α = 93.177(10)°, β = 101.691(10)°, γ = 113.995(9)°, V = 931.8(2), Z = 2). Two crystallographically independent hexachlororhodate ions, three crystallographically independent guanidinium ions and one water molecule are linked by a complex framework of hydrogen bonds.
Chemistry of the 1,3,5-Triaza-2-phosphorin-4,6-diones, Part XII*. Synthesis and Characterization of 2-PhenyI-2-(p-tolylthio)-1,3,5- trimethyI-1,3,5-triaza-4,6-dione-2-phosphorinonium Salts
Authors: Pinchuk Vasily A . , Neda Ion , Müller Christian , Thönnessen Holger , Jones Peter G. , Schmutzler Reinhard
Published: February 2015

The reaction of 1,5-bis(trimethylsilyl)-1,3.5-trimethylbiuret (1) with p-tolylsulfenyl chloride (2) furnished l-(p-tolylthio)-5-trimethylsilyl-1,3,5-trimethylbiuret (3). In the reaction of 3 with phenyldichlorophosphine, 2-phenyl-2-(p-tolylthio)-1,3,5-trimethyl-1,3,5-triaza-4,6-dione- 2-phosphorinonium chloride (4) was formed. The same product was obtained from the reaction of 2-phenyl-1,3,5-trimethyl-1,3,5-triaza-2λ3- phosphorin-4,6-dione (6) with p-tolylsulfenyl chloride (2). Compound 4 was isolated and characterized in the form of the hexachloroantimonate (4a). The spirophosphorane 2-phenyl-1,3,5-trimethyl-1,3,5-triaza-7,10-dioxa-8,9- perchlorobenzo-2λ5-phosphaspiro-[4.5]decan-4,6-dione (7) was prepared by the reaction of 4 with tetrachloroorthobenzoquinone. The new products were characterized by 1H - and 13C NMR spectroscopy, elemental analysis, 31P NMR spectroscopy in the case of 4a. 6 and 7, and mass spectrometry (4a). Single-crystal X-ray structural analyses of compounds 4a and 7 were conducted. The phosphorus atom of 4a has the expected tetrahedral geometry, with a rather short P-S bond of 204.9(2) pm. In 7 the geometry at phosphorus is almost ideal trigonal bipyramidal. Weak hydrogen bonds are formed from a C (:O) group to deuterochloroform of solvation.
Metallkomplexe mit funktionalisierten Schwefelliganden, XI [1] Herstellung von 5H-Benzo[f]-1,2,3,4-tetrathiepin-1-oxid und 1,2-Benzo-4,5,6,7-tetrathiocin-4-oxid und Reaktionen mit Platin(0)-Komplexen / Metal Complexes of Functionalized Sulfur Containing Ligands, XI [1]Synthesis of 5H-Benzo[f]-1,2,3,4-tetrathiepin-1-oxide and 1,2-Benzo-4,5,6,7-tetrathiocin-4-oxide and their Reactions with Platinum (O) Complexes
Authors: W eigand W olfgang , Wünsch Ralf , Dick Stefan
Published: February 2015

5H-Benzo[f]-1,2,3,4-tetrathiepin-1-oxid e 5 and 1,2-Benzo-4,5.6,7-tetrathiocin-4-oxide 6 have been prepared by oxidation of the corresponding tetrasulfides 3 and 4, respectively using mCPBA in dichloromethane. The unstable bright yellow crystals of 5 were characterized by an X-ray structure determination. Lattice dimensions: a = 843,2(4), b = 468,9(2). c = 2409.5(14) pm. b = 95,19(4)°; space group P2,/n, Z = 4. The platinum(O) compounds L2Pt(η2-C2H4) [7a: L = 1/2 Fe(η5-C5H4PPh2)2, 7b: L = (-)-DIOP] react with the tetrasulfide oxides 5 and 6 to give products of an oxidative addition of sulfur, the sulfido bridged diplatinum complexes [L2Pt(μ-S)]2 [8a: L = 1/2 Fe(η-C5H4PPh2)2, 8b: L = (-) - DIOP] . When the reaction is carried out with 6 and 7b, the thiosulfinate 9 is identified together with 8b. The former is a co-product of the desulfurization followed by a ring-contraction of 6.
Synthesis of Cyclopropanated Dimethyl Mercaptal Sulfoxide Pyranoses from Epoxytriflate Pyranosides and Methyl Methylthiomethyl Sulfoxide
Authors: Khan Noshena , Kohlbau Hans-Jürgen , Voelter Wolfgang
Published: February 2015

The reaction of 4-O-triflyl-2-3-anhydropyranosides with metyl methylthiomethyl sulfoxide in the presence of n-BuLi or NaH affords 3,4-cyclopropanated pyranosides via triflate substitution and subsequent intramolecular epoxide opening.
Transition Metal Complexes of Diazenes, XXXVIII [1] Activation of Aromatic C-Cl Bonds in the Oxidative Addition of ortho-Chlorophenyldiazenes to Chlorotris(triphenylphosphine)rhodium
Authors: Aulwurm Uwe R. , Knoch Falk , Kisch Horst
Published: February 2015

Refluxing a slightly acidic n-BuOH solution of RhCl(PPh3)3 and 2-chloro-, 2,4-dichloro-, or 2,4,6-trichloroazobenzene affords cyclometalated complexes (1) via loss of one phosphine ligand and oxidative addition of the ortho -C-Cl bond. X-ray structural analysis indicates a trans-position of the two triphenylphosphine ligands. The reaction proceeds only in polar solvents like alcohols or dimethyl sulfoxide but not in toluene. In the presence of air or oxygen a hydrido complex was formed as a by-product.
Darstellung, 11 B-NMR-, Schwingungsspektren und Kristallstruktur von Bis(tetraphenylphosphonium)-2-[2-(2-pyridyl-amino)-pyrid-5-yl]-closo-decaborat, [P(C6H5)4]2[2-{2-(2-(C5H4N)-NH)-(C5H3N)-5}B10H9] / Preparation, 11B NMR, Vibrational Sprectra and Crystal Structure of Bis(tetraphenylphosphonium) 2-[2-(2-Pyridyl-amino)-pyrid-5-yl]-closo-decaborate, [P(C6H5)4]2 [2-{2-(2-(C5H4N)-NH)-(C5H3N)-5}B10H9]
Authors: Nachtigal C. , Preetz W.
Published: February 2015

By reaction of [N(C4H9)4]2[B10H10] with 2, 2′-(C5H5N)2NH at 160 °C the 2-[2-(2-pyridylamino)- pyrid-5-yl]-closo-decaborate anion [2-{2-(2-(C5H4N)-NH)-(C5H3N)-5 }B10H9]2− is obtained which can be separated from excess [B10H10]2− by ion exchange chromatography on diethylaminoethyl(DEAE) cellulose. The crystal structure of [P(C6H5)4]2[2-{2-(2-(C5H4N)- NH)-(C5H3N)-5 }B10H9] has been determinated by single crystal X-ray diffraction analysis: monoclinic, space group P21/n with a = 11.435(3), b = 22.923(2), c = 20.094(4) Å, β = 95,27(2)°, Z = 4. By influence of the substituent the B10 cage is strongly distorted with B-B distances ranging from 1.522 to 2.188 Å. The 11B NMR spectrum reveals the feature (2:1:7) of a B10 cage with the substituent in the 2 position with a downfield shift of the ipso B atom at −20.2 ppm. The IR and Raman spectra exhibit characteristic BH stretching vibrations between 2416 and 2499 cm −1 and the (C-C) and (C-N) stretching vibrations in the range of 1306 to 1584 cm −1 .
Zur Umsetzung von Bis(η5-cyclopentadienyl)dihydridowolfram mit Halogenboranen / On the Reaction of Bis(η5-cyclopentadienyl)tungstendihydride with Boran Halides
Authors: Braunschweig Holger , Wagner Trixie
Published: February 2015

Bis(η5 -cyclopentadienyl)tungstendihydride reacts with iPr2BCl, BCl3 or BF3 to give the saltlike compounds [Cp2WH3]iPr2BCl2 (1a), [Cp2WH3]BCl4 (b), and [Cp2WH3]BF4 (c) with a bis(η5-cyclopentadienyl)trihydridotungsten cation and a borate anion. Compound 1a crystallizes in the space group P21/n.
Synthesis, Solution, Molecular and Crystal Structure of Bis[5-(coproporphyrinato-I tetraethylester)nickel(II)]1,2-ethane
Authors: Senge Mathias O. , Ponomarev Gelii V. , Forsyth Timothy P. , Smith Kevin M.
Published: February 2015

Vilsmeier formylation of the oporphyrin-I tetraethyl ester Ni-complex (III) followed by reduction of the intermediary imine salt (IV) with NaBH4 gave the o-dimethylaminomethyl-coproporphyrin-I Ni-complex (V). Heating the latter in methyl iodide gave 65% of the ethane- bis-porphyrin (I), which has been characterized by NMR-spectroscopy and a molecular and crystal structure investigation. The crystal structure shows an extended structure of the bisporphyrin with a parallel arrangement of the porphyrin subunits. Crystal data: I - C90H106N8Ni2O16. Triclinic, a = 12.319(3) Å. b = 13.297(3) Å, c = 14.444(3) Å, α = 105.56(2)°, β = 100.82(2)°, γ = 112.98(2)°, V = 1981.0(7) Å3, Cu Kα radiation, λ = 1.54178 Å, space group P1̄, Z = 1, R = 0.07.
Notizen: Polysulfonylamine, LXXVIII [1] 1-Mesyl-4 -dimethylaminopyridinium - dimesylamid: Darstellung und Festkörperstruktur / Polysulfonylamines, LXXVIII [1] 1-Mesyl-4-dimethylaminopyridinium Dimesylamide: Synthesis and Solid State Structure
Authors: Wirth Andreas , Blaschette Armand , Jones Peter G.
Published: February 2015

Treating (MeSO2)3N with 4-dimethylaminopyridine in MeCN afforded the ionic title compound (monoclinic, space group P21/c). The bond lengths of the 4-dimethylaminopyridinium moiety suggest a semiquinoid resonance form with a double bond to the exocyclic nitrogen and two localized carbon-carbon double bonds in the ring. The ring and the exocyclic N and S atoms of the cation are essentially coplanar. The S -N bond distances in the cation (173.4 pm) and the anion (159.1 and 159.6 pm) correlate with Pauling bond orders of 1.0 and 1.7, respectively. The anion displays a staggered conformation with approximate C2 symmetry ( S - N -S 120.4°).
Gold(I) Complexes of Chiral Secondary Phosphines
Authors: Angermaier Klaus , Sladek Alexander , Schmidbaur Hubert
Published: February 2015

The reaction of (dimethylsulfide)gold(I) chloride and bromide with methyl(phenyl)phosphine in ṯetraẖydrof̱uran affords high yields of the colorless, crystalline, chiral complexes [Me(Ph)HP]AuCl/Br ( 1a, b). Treatment of la with potassium iodide in thf leads to a conversion into the corresponding iodide [Me(Ph)HP] Aul ( 1c). The compounds were characterized by their analytical and spectroscopic data, and the crystal structures of la, b have been determined. The two compounds are isomorphous. In the lattice the monomers form chain-like supramolecular aggregates through auriophilic Au-Au contacts. The chains contain both enantiomers following the sequence ..R S R S R S.., with the individual components related by crystal symmetry.
Synthesis and Characterization of Bis(3-chloro-4-dodecyloxyphenyl) Malondialdehyde Complexes of Cu(II) and Ni(II)
Authors: Salas-Reyes V. , Soto-Garrido G. , Aguilera C.
Published: February 2015

Bis (3-chloro-4-dodecyloxyphenyl) malondialdehyde copper(II), as well as its nickel(II) homologue have been synthesised. The copper(II) complex shows a narrow (15 °C) nematic phase below its clearing temperature. The nickel(II) complex is polymeric in nature.
Untersuchungen zur Säurestärke von Alkanpolysulfonsäuren / Investigations on the Acid-Strength of Alkanepolysulfonic Acids
Authors: Jüschke Ralf , Sartori Peter
Published: February 2015

The acid strength of alkanepolysulfonic acids was measured using the correlation between the 29Si NMR shift of the corresponding trimethylsilylester of an acid and the pKS1-value of the acid. Alkanepolysulfonic trimethylsilylesters XHC(SO3-SiMe3)2, X2C(SO3-SiMe3)2, XC(SO3- SiMe3)3 and Me3Si-O3S-(CR2)n-SO3-SiMe3 with X = H, F, Cl, Br, I and R = H, F and n = 1 - 5 were investigated.
Metallkomplexe mit Cyanoguanidin als Liganden: Kristallstrukturen von [Cd(cnge)2F2]·3H2O , Cd(cnge)2Br2 und Hg(cnge)Cl2 (enge = C yanoguanidin) / Metal Complexes with Cyanoguanidine as Ligand: Crystal Structures of [Cd(cnge)2F2]·3H2O, Cd(cnge)2Br2 and Hg(cnge)Cl2 (cnge = Cyanoguanidine)
Authors: Pickardt Joachim , Kühn Britta
Published: February 2015

Crystals of [Cd(cnge)2F2]·3H2O (1), Cd(cnge)2Br2 (2) and Hg(cnge)Cl2 (3) (cnge = cyanoguanidine) were obtained by crystallisation from solutions of CdF2, CdBr2 or HgCl2 and cyanoguanidine in water/ethanol or methanol. 1 crystallizes monoclinically, space group C2, Z = 2,a = 1629.2(4), b = 1056.6(4), c = 353.9( 1) pm, β = 101.05(2)°; 2 is monoclinic, space group P21/n, Z = 2, a = 391.9(1), b = 850.7(2), c = 1722.1(4) pm, β = 94.06(2)°, 3 is triclinic, space group P1, Z = 1, a = 686.7( 1), b = 693.0(5), c = 387.2(4) pm, α = 94.45(5)°, β = 95.05(4)°, γ = 78.58(5)°. In 1 and 2 each Cd atom is bonded to four halogen atoms to form polymeric (CdF2)n and (CdBr2)n chains, resp., and to two cyanoguanidine molecules. In 3 each Hg atom is bonded to four chlorine atoms also forming (HgCl2)n chains, which are connected via cyanoguanidine molecules acting as a bidentate bridging ligands to form a network.
Synthese, Kristallstruktur und Eigenschaften von 1,1,1,3,3, 3 - Hexaamino - 1λ5,3λ5-diphosphazeniumehlorid [(NH2)3PNP(NH2)3]Cl / Synthesis, Crystal Structure, and Properties of 1,1,1,3,3,3-Hexaamino- 1λ5 ,3λ5-diphosphazenium Chloride [(NH2)3 PNP(NH2)3 ]Cl
Authors: Horstmann Stefan , Schnick Wolfgang
Published: February 2015

[(NH2)3PNP(NH2)3]Cl has been prepared by a three step synthesis. The last step is the ammonolysis of [Cl3PNPCl3]Cl. Single crystals of 1,1,1,3,3,3-hexaamino-1λ5, 3λ5-diphosphazenium chloride were obtained from an acetonitrile solution in a temperature gradient between 60 °C and room temperature. Between room temperature and -100 °C [(NH2)3PNP(NH2)3]Cl is subject to a phase transition. Therefore, the crystal structure was determined by single crystal X-ray methods at room temperature (P1̄, a = 584.7(1) pm, b = 732.1(1) pm, c = 1092.0(2) pm. q = 71.05(3)°, β = 76.36(3)°, γ = 89.83(3)°, Z = 2, R = 4.75 %, wR = 2.47 %). The cation [(NH2)3PNP(NH2)3]+ is built up by two corner sharing PN4 tetrahedra. Remarkably short P-N bonding distances have been observed and both PN4 tetrahedra exhibit a significant distortion resulting in two large and four small N-P-N bond angles.
N-Iod-triphenylphosphanimin. Synthese und Kristallstrukturen von [Me3SiNPPh3· ICl] und Ph3PNI / N -Iodo-triphenylphosphaneimine. Synthesis and Crystal Structures of [Me3SiNPPh3 · ICl] and Ph3PNI
Authors: Grebe Jutta , Weller Frank , Dehnicke Kurt
Published: February 2015

N-Iodo-triphenylphosphaneimine, Ph3PNI, has been prepared by thermolysis of the donor acceptor complex [Me3SiNPPh3·ICl] in boiling acetonitrile in the presence of potassium fluoride. Both compounds have been characterized by IR spectroscopy and by crystal structure determinations.

[Me3SiNPPh3 · ICl]: Space group P1̄, Z = 2, a = 888.3(1), b = 1070.7( 1), c = 1310.2( 1) pm, α = 95.15( 1)°, β = 108.67( 1)°, γ = 97.78( 1)° at 20°C. The complex has a molecular structure in which the N atom of the phosphaneimine is connected with the iodine atom of the ICI molecule in a linear arrangement N-I-Cl with bond lengths N-I = 232.7 pm, I-Cl = 255.37 pm. \

Ph3PNI: Space group P21/n, Z = 4, a = 952.8(1), b = 1800.8(2), c = 1003.6(1) pm, β = 110.25(1)° at -50°C. The compound forms monomeric molecules with bond lengths PN = 159.1 pm, I-N = 205.6 pm and an INP bond angle of 113.3°.
Synthesis of a New bis-Harmine Selenide
Authors: Khan M. Ataullah , Raees Humaira
Published: February 2015

Harmine ( 1) upon refluxing with selenium dioxide in acetic acid for 15 hours yielded bisharmine selenide (4) via the intermediates 2 and 3.
Regio- und Stereoselektive Ringöffnung von Epoxypyranosiden durch Isopropoxytitanreagenzien und Sml2: Ein einfacher Zugang zu Ioddesoxyzuckern / Regio- and Stereoselective Ring Opening of Epoxy Pyranosides with Titanium Isopropoxide Reagents and Sml2: A Straightforward Access to Iododeoxy Sugars
Authors: Khan Noshena , Al-Abed Yousef , Kohlbau Hans-Jürgen , Latif-Ansari Farzana , Kowollik Wolfgang , Voelter Wolfgang
Published: February 2015

A regioselective synthesis of 3-iodo-3-deoxy sugars is described by trans-diaxial cleavage of the oxirane ring of 2.3-anhydropyranosides with halogenated titanium isopropoxide reagents and samarium iodide.
Molecular Structure of Tri(2-thienyl)borane
Authors: Wrackmeyer Bernd , Milius Wolfgang , Molla Elias
Published: February 2015

The molecular structure of tri(2-thienyl)borane (1) was determined [monoclinic, space group P21/ c; a = 12.216(2), b = 7.765(2), c = 12.605(2) Å, β = 93.13(2)°]; two of the three thienyl groups are disordered, as is also indicated by the solid-state 13C CP/MAS NMR spectrum of 1. The 13C NMR spectra of 1 were measured at variable tem perature in solution and the barrier to rotation about the B-C bonds was found to be <35 kJ/mol. Thus, CB(pp)π interactions must be regarded as rather weak, in spite of suggestive δ11 B. δ13C data and structural parameters.
Synthesis and Structure of Li4GeS4
a
Authors: Matsushita Yoshitaka , Kanatzidis Mercouri G.
Published: February 2015

The compound Li4GeS4 has been prepared as transparent, light yellow moisture-sensitive crystals. Li4GeS4 belongs to the space group Pnma with a = 14.107(6) Å, b = 7.770(3) Å and c = 6.162(2) Å. The crystal structure was solved by direct-methods. The final R and Rw-values are 1.85 and 1.65% for 866 observed reflections. The Li4GeS4 structure has three crystallographically independent lithium sites and one germanium site. The lithium atoms adopt two different coordination types. The Li l atom is coordinated to five sulfur atoms in a square pyramidal geometry, while the Li2 and Li3 atoms have distorted tetrahedral coordination. The Ge atom is tetrahedrally coordinated by four sulfur atoms and is found as [GeS4]4- units. The anisotropic three-dimensional crystal structure of Li4GeS4 is described.
Magnetische Eigenschaften von [Cu{OCH2CH2N(C4H9)2}NCO]4 im Bereich von 10 bis 240 K / Magnetic Properties of [Cu{OCH2CH2N(C4H9)2}NCO]4 in the Temperature Range from 10 to 240 K
Authors: Münch W. , Walz L. , König M.
Published: February 2015

The magnetic properties of the title compound were re-investigated, since a new phase below 240 K has recently been identified. The exchange parameters were evaluated from the temperature dependence of the magnetic susceptibility with a Heisenberg operator taking into account the high pseudo-symmetry of the tetrameric units observed.
Synthese und Kristallstruktur des Lanthan-Titanat-Tellurats LaTi(Ti0,25Te0,75)O6 und seine Verwandtschaft mit PbSb2O6 und Sr(MnTe)O6/Synthesis and Crystal Structure of the Lanthanum Titanate Tellurate LaTi(Ti0.25Te0.75)O6 and its Relationship to PbSb2O6 and Sr(MnTe)O6
Authors: Wulff L. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of LaTi(Ti0.25Te0.75)O6 have been prepared by solid state reactions. X-ray investigations led to trigonal symmetry, space group C3
1-P3 , a = 5.141(10), c = 5.218(10) Å, Z = 1. The compound is characterized by a predominantly ordered distribution of Ti4+ and Te6+. Typical features of the crystal structure are staggered layers containing edge connected TiO6 and (Ti,Te)O6 octahedra. The layers are connected by La3+ ions receiving an octahedral coordination by the surrounding oxygen ions. The relationships to the PbSb2O6 type and the recently described compound Sr(MnTe)O6 are discussed.
Oxochlorierung von Übergangsmetall-Komplexen mit Thionylchlorid/Oxochlorination of Transition Metal Complexes with Thionyl Chloride
Authors: Stoll Carola , Lorenz Ingo-Peter , Nöth Heinrich , Seifert Thomas
Published: February 2015

The reaction of the transition metal complexes CpV(CO)4 and [CpMo(CO)3]2 with thionyl chloride affords the oxodichlorides CpM(O)Cl2 (M = V, Mo) by oxidative decarbonylation. The X-ray structure analysis of CpV (O)Cl2 shows the pseudo tetrahedral “piano-stool” configuration for the central vanadium atom.
Ag2Cs[B15O24]: Ein wasserfreies quaternäres Silber(I)-Borat mit einem neuartigen Boratanion mit helixartigem Aufbau / Ag2Cs[B15O24]: An Anhydrous Quaternary Silver(I)-Borate with a New Helical Borate Anion
Authors: Wiesch A. , Bluhm K.
Published: February 2015

Single crystals of Ag2Cs[B15O24] were prepared by using a B2O3 flux technique with Ag2CO3 and Cs2CO3 in a closed silver tube at 650 °C. X-Ray investigations led to a new crystal structure in the space group P 21212 (Nr. 18) with lattice parameters a = 1778.7 (4); b = 2219.2 (4); c = 512.2 (1) pm, Z = 4. The silver atoms are part of distorted AgO4 tetrahedra and planar AgO3 units while the caesium atoms are eightfold coordinated by oxygen. The compound contains an as yet unknown borate anion [B15O24] with twelve BO3- and three BO4 units per formula. The BO3 units are connected to eight cords twisted to helices which are combined via BO4 tetrahedra to a three dimensional framework with large tunnels occupied by the cations.
Zum Chemischen Transport von Rhenium und Rheniumoxiden/On the Chemical Transport of Rhenium and Rhenium Oxides
Authors: Feller J. , Oppermann H. , Binnewies M. , Milke E.
Published: February 2015

Synthesis and single crystal growth by chemical transport reactions of rhenium and rhenium oxides is reported. Several transport agents like the mercury halides HgCl2, HgBr2, HgI2, tellurium tetrachloride and iodine have been employed the transport of the rhenium compounds. Mass spectrometric experiments gave informations about the composition of the gas phase. The transport reactions were traced by calculations based on the knowledge of the gas phase species and their thermodynamical data.
Darstellung und Schwingungsspektren von cis- und trans-[OsXY(acac)2], X ≠ Y = Cl, Br, I sowie Normalkoordinatenanalyse von trans-[OsClBr(acac)2]/Synthesis and Vibrational Spectra of cis- and trans-[OsXY(acac)2], X ≠ Y = Cl, Br, I, and Normal Coordinate Analysis of trans-[OsClBr(acac)2]
Authors: Dallmann K. , Preetz W.
Published: February 2015

In the reaction of K2[OsX3 Y3] with boiling water/acetylacetone (1:1) the six mixed com­plexes cis-and trans-[OsX2 (acac)2] (X ≠ Y = Cl, Br, I) are formed, which have been purified by column chromatography with toluene on silica gel. The IR and Raman spectra (10K) show the intraligand vibrations of the acac groups with nearly constant frequencies and the stretching vibrations of OsO in the range 460-696, of OsCl at 315-345, of OsBr at 210-225, and of Osl at 160-175 cm-1 . A normal coordinate analysis based on a modified valence force field was performed for trans-[OsClBr(acac)2] and the vibrational modes have been assigned. With a set of 32 force constants, taking into account the intraligand vibrations, a good agreement between observed and calculated frequencies has been achieved. The valence force constants are fd (OsCl•) = 1.75, fd(OsBr′) = 1.63 and fd (OsO) = 3.27 mdyn/Å.
Interaction of the Vanadyl(IV) Cation with L-Ascorbic Acid and Related Systems
Authors: Ferrer E. G. , Williams P. A . M. , Baran E. J.
Published: February 2015

The interaction of VO2+ with L-ascorbic acid and dehydroascorbic acid was investigated by electronic spectroscopy in solution at different pH values. In the case of ascorbic acid, two different solid complexes containing one or two monodeprotonated ascorbate ligands could be isolated and characterized. With dehydroascorbic acid, interaction begins at pH = 4 but at higher pH values the ligand is hydrolysed irreversibly, generating 2,3-diketogulonic acid. A solid complex containing this ligand could be precipitated at pH = 7. Its spectroscopic behavior confirms the interaction of the cation with an enolised form of the acid.
Isolierte trigonale SrO6 – Prismen verknüpfen Kagome-Netze im Strontium-Manganat(IV)-Tellurat(VI): SrMnTeO6 / Kagomé Layers Connected by Isolated Trigonal SrO6 Prisms in the Strontium Manganate(IV) Tellurate(VI): SrMnTeO6 L
Authors: Wulff L. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of the hitherto unknown compound SrMnTeO6 have been prepared from Sr(OH)2 ·8H2O , MnCO3(aq) and TeO2 in air by crystallization below the melt range. X-ray investigations showed hexagonal symmetry, space group D3
3h -P6̅2m, lattice constants a = 5.143( 1), c = 5.384(2) A, Z = 1. SrMnTeO6 is characterized by staggered [(Mn/Te)6O18] Kagome layers along [001]. These layers are connected by Sr2+ ions, resulting in SrO6 prisms isolated from each other. The structure is discussed with respect to the connection of Kagome nets in the quaternary oxides of the Ba3Ln4O9 type.
Kristallstruktur von [Mo(Co)3(Ncme)(Srbu)]2 / Crystal Structure of [Mo(CO)3(NCMe)(S'Bu)]2
Authors: Kopp Mike R. , Neumüller Bernhard
Published: February 2015

Single crystals of [Mo(CO)3(NCMe)(S′Bu)]2 (1) and [{Mo(CO)3}2{Mo(CO)2}{S′Bu}4] (2) were obtained by the reaction of [Mo(CO)3(NCMe)3] with [(PhCH2)2GaS′Bu]2 in 1,4-dio-xane. The X-ray structure determination of 1 showed the presence of a Mo2S2 four-membe-red ring with a Mo-Mo bond length of 296,7(1) pm. Space group Pbca, Z = 4, lattice dimen­sions at -80°C: a = 1588,2(3), b = 905,8(1), c = 1676,0(1) pm, R1 = 0,0555.
Experimental and Computational Studies on Aminoguanidine Free Base, Monocation and Dication. Part III: Proton Affinities of Guanidine, Aminoguanidine and Glyoxal Bis(amidinohydrazone)
Authors: Koskinen Jere T.
Published: February 2015

The structures of glyoxal bis(amidinohydrazone) (GBG) free base and glyoxal bis(amidi-nohydrazonium) monocation and dication were calculated quantum chemically by using the density functional hybrid method B3-LYP with the standard basis set 6 -31 G (d). Proton affinities calculated from these data are 246.4 kcal/mol for the free base and 176.0 kcal/mol for the monocation. The proton affinities of guanidine free base (246.2 kcal/mol), aminogua­nidine free base (242.9 kcal/mol), aminoguanidinium monocation (88.6 kcal/mol) were calcu­lated for reference. The B3-LYP functional overestimates the proton affinities for all the species studied. For example, for guanidine the proton affinity at the M P2/6-31G (d) level is 238.3 kcal/mol, the experimental reference value being 233 kcal/mol. However, from the B3-LYP values it can be concluded that in the gas phase all the three bases are nearly equally basic. On the other hand, it is known that in aqueous solution guanidine is a much stronger base than aminoguanidine and glyoxal bis(amidinohydrazone). The results are discussed from the point of view of molecular size, shape and symmetry, and hydrogen bonding in solution.
Synthesis and Structure of Benzyltriethylammonium Trichlorogermanate(II)
Authors: Wegner Gerald L , Jockisch Alexander , Schmidbaur Hubert
Published: February 2015

The reaction of equimolar quantities of GeCl2 · dioxane with [BzEt3N]+ Cl- in tetrahydro-naphthaline gives high yields of [BzEt3N]+ [GeCl3]-. The asymmetric unit of the monoclinic single crystals (from CH2CI2 , space group P21/c, Z = 8) are comprising two pairs of crystallographically independent cations and anions, each with very similar molecular dimensions. The isolated [GeCl3]-anions have a trigonal pyramidal structure with narrow Cl-Ge-Cl angles in the range from 93.41(5) to 98.27(5)° and Ge-Cl distances between 2.293(2) and 2.305(2) Å. This structure is thus very similar to that of the isoelectronic AsCl3 molecule and of the [SeCl3]+ cation.
Untersuchungen An Natriumtrifluormethylsulfonat. Kristallstruktur von Natriumtrifluormethylsulfonat- Trifluormethylsulfonsäure (1/3) / Studies on Sodium Trifluoromethanesulfonate. Crystal Structure of Sodium Trifluoromethanesulfonate-Trifluoromethanesulfonic Acid (1/3)
Authors: Korus Gabriele , Jansen Martin
Published: February 2015

Single crystals of sodium trifluoromethanesulfonate-trifluoromethanesulfonic acid (1/3) (NaSO3CF3 · 3 HSO3CF3) have been prepared by reaction of sodium trifluoromethanesulfonate with anhydrous trifluoromethanesulfonic acid at 60 °C. NaSO3CF3 · 3 HSO3CF3 crystallizes in space group I213 (No. 199) with a = 16.210(1) Å, Z = 8. Sodium is coordinated by six oxygen atoms from six different trifluoromethanesulfonic acid molecules, each acid molecu­le connecting two sodium ions. The 3-dimensional network resulting from the edge sharing octahedra corresponds to the cubic (10, 3) net, not realised otherwise, so far. The trifluorome­thanesulfonate anion is bonded to three trifluoromethanesulfonic acid molecules by hydrogen bonds.
Ein weiteres 2λ5,4λ5-Diphosphapyridin: 2,2,4,4-Tetrakis-(dimethylamino)-6- amino-1-aza-2λ5,4λ5-diphosphinin / A Further 2λ5,4λ5-Diphosphapyridine: 2,2,4,4-Tetrakis-(Dimethylamino)-6-amino-1-aza- 2λ5,4λ5-diphosphinine
Authors: Heckmann Gemot , Jonas Ekaterina , Fluck Ekkehard , Neumüller Bernhard
Published: February 2015

2,2,4,4-Tetrakis-(dimethylamino)-6-amino-1-aza-2λ5,4λ5-diphosphinine (3) has been prepared by reacting 1,1,3,3-tetrakis(dimethylamino)-1λ5-3λ5-diphosphete (1) with bis(trimethylsilyl) carbodiimide (2) in a 2 : 1 molar ratio. Properties, 1H, 31P, and 13C NMR, mass, and IR spectra are reported and discussed. Compound 3 is further characterized by X-ray structure analysis.
Structure of the Short-Lived Intermediate Formed during the Metal Substitution Reaction of the Mercury(II) Porphyrin Complex with Cobalt(II) Ion in Aqueous Solution Determined by the Stopped-Flow EXAFS Method
Authors: Ozutsumi Kazuhiko , Ohnishia Shintaro , Ohtaki Hitoshi , Tabatab Masaaki
Published: February 2015

The local structure around the cobalt(II) ion in the reaction intermediate formed during the metal substitution reaction of the homodinuclear mercury(II) porphyrin (5,10,15,20-tetrakis(4- sulfonatophenyl)porphyrin; H2tpps4- ) complex with a cobalt(II) ion in an acetate buffer has been determined by the stopped-flow EXAFS method. The structure of the reactant and the product of the above reaction has also been determined by the same method. The coordination geometry around the cobalt(II) ion in the heterodinuclear intermediate, [Hg(tpps)Coll]2- , is six-coordinate octahedral with four additional water and/or acetate oxygen atoms. The Coll-N and Coll-O bond lengths in the intermediate are 212(2) and 221(1) pm, respectively. The product, [Coll(tpps)]4-, has a six-coordinate octahedral structure, the Coll-N and Coll-O bond lengths being 203(1) and 215(1) pm, respectively. The Coll-N bond length in the intermediate is ca. 9 pm longer than that in the product. The Coll-O bond length in the intermediate is also ca. 9 pm longer than that of 212(1) pm in the reactant, the cobalt(II) acetato complex, and ca. 6 pm longer than that in the product. The longer Coll-O bond in the intermediate as compared to those in the reactant and in the product appears to be responsible for the instability of the intermediate. The oxidized product, [Colll(tpps)]3-, has a six-coordinate structure with two additional Colll-O bonds. The Colll-N and Colll-O bond lengths are 189(1) and 197(2) pm, respectively, and are much shorter than those in [Coll(tpps)]4-.
Carbacylamidophosphates: Synthesis, Properties, and Structure of Dimorfolido-N-trichloroacetylphosphorylamide
Authors: Ovchynnikov Vladimir A , Amirkhanov Vladimir M , Timoshenko Taras P , Glowiak Tadeusz , Kozlowskib Henryk
Published: February 2015

Dimorpholido-N-trichloroacetylphosphorylamide: CCl3C(O)NHP(O)[N(CH2CH2)2O]2 [HL] and its sodium [NaL] and morpholine [HN(CH2-CH2)2O•HL] salts were synthesized for the first time. The compounds were studied by IR spectroscopy and assignments of the characteristic IR bands have been made. The structure of [HL] was determined by X-ray diffraction. Crystals are monoclinic, a = 11.412(2) Å, b = 16.056(3) Å, c = 9.622(2) Å, β = 108.55(3)°, space group P21/c; Z = 4. The refinement of the structure converged at R = 0.066. The molecules are connected into centrosymmetric dimers via hydrogen bonds formed by the phosphorylic oxygen atoms and hydrogen atoms of amide groups.
The Partial Oxidation of Methane to Methanol with Nitrite and Nitrate Melts
Authors: Lee Bor-Jih , Kitsukawa Shigeo , Nakagawa Hidemoto , Asakura Shukuji , Fukuda Kenzo
Published: February 2015

The effect of reduced oxygen species on the partial oxidation of methane to methanol was examined with nitrite melts. The experimental results support the suggestion that the formation of methanol or C2 compounds depends on different reduced oxygen species, as observed in our previous work using nitrate melts. It has been suggested that the partial oxidation of methane proceeds to CH3OH or C2 compounds via parallel pathways. This suggestion was verified by increasing the oxygen concentration to carry out the partial oxidation of methane in 25 mol% NaNCO3 -75 mol% KNO3 melts. A methanol selectivity of 8.2% and a methanol yield of 0.43% were observed with CH4/O2 = 15/1 at 575 °C, whereas with CH4/O2 = 7/1 methanol selectivity and yield increased to 23.7% and 1.1%, respectively. The results further confirm the contribution of the superoxide ion O2
- on methanol formation.
Dioxomolybdän(VI)-Komplexe mit dreizähnigen diaciden Liganden / Dioxomolybdenum(VI) Complexes with Tridentate Diacidic Ligands
Authors: Banße Wolfgang , Fliegner Jana , Sawusch Stefan , Schilde Uwe , Uhlemann Erhard
Published: February 2015

Dioxomolybdenum(VI) complexes have been synthesized by ligand exchange reactions of Mo(CO)6, Mo(NO)2(acac)2 and MoO2(acac)2 with tridentate diacidic ligands. X-ray structure analyses were performed on single crystals. The complexes salicylaldehyde-2-hydroxyanilato(2-)-triphenylphosphaneoxide-dioxomolybdenum(VI) (1b) and 2,2'-dihydroxy-azobenzenato(2-)-triphenylphosphaneoxide-dioxomolybdenum(VI) (2) are isomorphous. In all chelates the Mo atom is in a distorted octahedral environment.

Structural data: Salicylaldehyde-2-hydroxyanilato(2-)-tetrahydrofurane-dioxomolybdenum (VI) (1a): a = 23.381(6) Å, b = 6.756(2) Å, c = 28.380(8) Å, β = 124.47(2)°; Salicylaldehyde-2-hydroxyanilato(2-)-triphenylphosphaneoxide-dioxomolybdenum (VI) (1b): a = 9.4208(14) Å, b = 30.550(5) Å, c = 10.461(2) Å, β = 111.005(17)°; 2,2′-Dihydroxy-azobenzenato(2-)-triphenylphosphaneoxide-dioxomolybdenum(VI) (2): a = 9.392(2) Å, b = 31.012(13) Å, c = 10.350(2) Å, β = 110.968(17)°; Salicylaldehyde-salicylhydrazonato(2-)-triphenylphosphaneoxide-dioxomolybdenum(VI) (3): a = 9.321(2) Å, b = 12.048(2) Å, c - 13.858(3) Å, α = 101.90(2)°, β = 94.94(2)°, γ = 105.479(17)°.
Synthesis, Spectroscopic Studies, and Crystal Structure of Diethylchlorotin Dimethylphosphinate Et2ClSnO2PMe2
Authors: Shihada Abdel-Fattah , Weller Frank
Published: February 2015

Diethylchlorotin dimethylphosphinate has been synthesized by treating (Et2ClSn)2O with HO2PMe2 in toluene. Single crystal X-ray analysis shows that O2PMe2 groups behave as bidentate bridge ligands between Et2ClSn units leading to a polymeric chain structure in which the tin atoms exhibit a distorted trigonal bipyramidal geometry with the oxygen atoms in the axial positions. The Sn-Cl bond lies on a C2 axis of symmetry in the (C2v) OCClSnCO unit. Et2ClSnO2PMe2 crystallizes in the monoclinic space group C2/c (a = 877.9 (2), b = 1907.8 (4), c = 695.5 (1) pm, β= 106.72 (2)°, Z = 4 and R = 0.043). The characteristic IR bands of Et2ClSnO2PMe2 are assigned and the mass spectrum is reported and discussed.
Studies on Tetramethylammonium Selenate(VI) and Chromate(VI)
Authors: Malchus Michael , Jansen Martin
Published: February 2015

[N(CH3)4]2SeO4 and [N(CH3)4]2CrO4 have been investigated by Infrared and Raman spectroscopy, coupled thermogravimetric and differential thermal analysis combined with mass spectroscopy of the evolved gases and temperature dependent X-ray diffraction. The crystal structure of [N(CH3)4]2SeO4 has been determined from single crystal data (cubic, Fm3̄m. a -11.1077(7) Å, Z = 4) and reveals [N(CH3)4]+ cations and SeO4
2- anions to be arranged in a Li2O -type of structure. While the cation framework of regular tetrahedra is orientationally fixed, the selenate anions are disordered. Powder diffraction data show [N(CH3)4]2CrO4 to be isostructural (cubic, Fm3̄m, a = 11,039(1) Å, Z = 4).
Stabile Carben-Addukte des Chlors / Stable Carbene Adducts of Chlorine
Authors: Kuhn Norbert , Fahl Joanna , Fawzi Riad , Maichle-Mößmer Cäcilia , Steimann Manfred
Published: February 2015

Abstract The carbene adducts 3a-c (R1 = Me, Et, iso-Pr; R2 = Me) are formed from the 2,3-dihydro-imidazol-2-ylidenes 1a-c and 1,2-dichloroethane as air-sensitive solids in good yields. The compounds exhibit a reactive Cl-Cl bond. Benzene is chlorinated by 3a,b to give chlorobenzene and the imidazolium salts 10a,b under mild conditions. 3c acts as a chloride donor to give with AICI3 and SO2 the 2-chloroimidazolium salts 12c and 13c (X = AlCl4, SO2Cl). On hydrolysis, the less reactive hydrate salt 14c is formed from 3c. The X-ray structures of 10a and 14c are reported.