bluuebunny/crossref_metadata_2025 huggingface dataset:
Synthesis of Methyl 6-Deoxy-6-diphenylphosphino-α-D-glucopyranoside: Temperature-Dependence of the Primary O-Tosyl Cleavage Mode
Authors: Dahlhoff Wilhelm V. , Radkowski Karin
Published: February 2015

Methyl α-D-glucopyranoside is converted to methyl 6-p-toluenesulfonyl-2,3,4-tris-O-trimethylsilyl- α-D-glucopyranoside 2 and then reacted with lithium diphenylphosphide in THF. When the reaction is carried out at room tem perature and below, S-O cleavage dominates giving methyl 2,3,4-tris-O-trimethylsilyl-α-D-glucopyranoside 3 , whereas at 60°C in THF or at 35°C in diethyl ether, C-O cleavage occurs yielding the title carbohydrate-phosphine 4 in good yield after deprotection
Neue Pnictide mit modifizierten AIB2-Strukturen / New Pnictides with Modified AIB2-Type Structures
Authors: Johrendt Dirk , Miericke Reiner , Mewis Albrecht
Published: February 2015

Nine new compounds AMX with A: Ca, Sr, Ba, M: Pd, Au and X:P, As were prepared by heating mixtures of the elements and investigated by Xray methods. They crystallize in modified AIB2- type structures, for the present examples in the ZrBeSi- and SrPtSb-types, with an ordered distribution of the atoms
Labilisierung einer Carboxylgruppe der koordinierten Triethylentetramin- N, N, N′,N″, N‴, N‴ -hexaessigsäure (H6ttha): Koordinationszahlen 10 für [La(H ttha)]2- und 9 für [Dy(Httha)]2- in ihren Guanidiniumsalzen / Labilizing of a Carboxyl Group o f the Coordinated Triethylenetetramine-N, N, N′ ,N″, N‴, N‴ - hexaacetic Acid (H6ttha): Coordination Numbers 10 for [La(Httha)]2- and 9 for [Dy(Httha)]2- in their Guanidinium Salts
Authors: Ruloff R. , Prokop Petra , Sieler J. , Hoyer E. , Beyer L.
Published: February 2015

The lanthanum(III) and dysprosium(III) complexes of triethylenetetramine-N, N, N′, N″, N‴, N‴-hexaacetic acid (H6ttha) were prepared and isolated as guanidinium salts:[C(NH2)3]2[La(Httha)] · 3 H2O and [C(NH2)3]2[Dy(Httha)] · 5 H2O. The X-ray crystal structure of both complexes was determined: In the La(III) complex (space group P1̄) all donor atoms (N4O6) are coordinated. The coordination number 10 is realized in a bicapped square antiprism (SAPRS-10). The bond length La to O of the protonated carboxylic group is ca. 0.3 Å longer than the other five La-O distances. The Dy(III) complex (space group P1̄) exhibits coordination number 9 in a monocapped square antiprism (SAPRS-9). The protonated carboxylic group is not coordinated.
Die Kristallstruktur von α-Heptanatrium-trihydrogennonawolframosilicat- Nonahydrat, α-Na7[H3SiW9O34]·9 H2O / Crystal Structure of α-Heptasodium-trihydrogennonatungstosilicate Nonahydrate, α-Na7[H3SiW9O34]-9 H2O
Authors: Hubert V. , Hartl H.
Published: February 2015

The title compound. α-Na7[H3SiW9O34]-9H2O. is the first a-isomer of heteropolyoxometalate anions [XW9O34]2-. Its crystal structure is interesting because of the unusual coordination chemistry of the Na+ cations and the formation of a microporous solid. While one of the three crystallographically independent Na+ cations is coordinated by oxygen atoms of the polyani­ons, the others form a cluster of four face-sharing sodium-oxygen-octahedra. The resulting microporous network contains large hexagonal channels.
Darstellung und Eigenschaften von zweikernigen Antimon(V)-Komplexen mit überbrückenden Benzylmethoxophosphonato-Liganden / Preparation and Properties of Binuclear Antimony(V) Complexes with Bridging Benzylmethoxophosphonato Ligands
Authors: Hornung H.-D. , Klinkhammer K. W. , Schmidt A.
Published: February 2015

The binuclear antimony(V) complexes Cl3Sb(0)[R3(R1O)PO2](OR2)SbCl3 with R1 = R2 = CH3 and R3 = p-ClC6H4CH2 (1), p-O2NC6H4CH2 (2) are prepared by reaction of the corre­sponding benzylmethoxophosphonic acids with antimony(v) chloride, water and methanol. 2 crystallizes in the orthorhombic space group Pnma with a = 1297.3. b = 1324.8, c = 1269.7 pm and Z = 4. The molecules of 1 and 2 are formed from two octahedra sharing one edge with antimony central atoms. Oxygen atoms are the links between the antimony atoms which are bridged by the bidentate phosphonato ligand. In solution the bridging phosphonato groups are inverted rapidly and the R2 groups undergo a slow intermolecular exchange. Two isomers can be detected by NMR spectroscopy.
Über die Reaktion von Chlornitrat ClONO2 mit PCl3, AsCl3, SbCl3 und AsCl4
+AsF6
- / On the Reaction of Chlorine Nitrate ClONO2, with PCl3, AsCl3, SbCl3 and AsCl4
+AsF6
-
Authors: Minkwitz Rolf , Hertel Thomas , Meier Ralf
Published: February 2015

The reaction of ClONO2 with PCl3 yields POCl3 and NO2
+NO3
- . With AsCl3 chlorine nitrate forms a compound of the analytical composition “AsCl2(NO3)3” in contrast to SbCl3, which does not react with ClONO2. The reaction of ClONO2 with AsCl4
+AsF6
- was reported to yield As(ONO2)4
+AsF6
-. We found no reaction below 273 K. Reaction at 293 K yields NO2
+AsF6
- as solid product. SbCl5 does react, but the reaction yields no reproduceable products.
Synthese und Umsetzungen von 4-Acyl/Carbamoyl-N-aryl-3-chloropyrrol-2,5-dionen: Kristallstruktur eines auf Wasserstoffbrückenbindungen basierenden supramolekularen Bandes [1] / Synthesis and Reactions of 4-Acyl/Carbamoyl-N-aryl-3-chloro-pyrrol-2,5-diones: Crystal Structure of a Supramolecular Ribbon Based on Hydrogen Bonds [ 1]
Authors: Saalfrank Rolf W. , Hörner Bernd , Reck Stephan , Nachtrab Jochen , Peters Eva-Maria , Peters Karl , Schnering Hans Georg von
Published: February 2015

Reaction of malondiamides 1 with oxalyl chloride (2) leads to the formation of 2,3-dioxo-2,3- dihydrofuran hydrochlorides 3 and 2,3-dioxo-2,3-dihydro-furanes 4, respectively. The structure of 3a was established by X-ray diffraction. The β-oxo-dibenzylamides 5 react with 2 regiospecifically to give the 2,3-dioxo-2,3-dihydrofuranes 6. Addition of water in 1,4-position to 6a yields hydroxy-enol 7, which forms bimolecular aggregates via intermolecular hydrogen bonds as shown by X-ray analysis. Intramolecular C,N-bisacylation of β-oxoamides 8 and malondiamides 11 with 2 leads to the pyrrol-2,5-diones 9 and 12. Reaction of the enols 9 and 12 with thionyl chloride leads to 3-chloro-pyrrol-2,5-diones 13. 3-Amino-pyrrol-2,5-diones 15 are obtained from 13 and amines 14, while 1, ω-diamines 16 yield the bispyrrol systems 17. X-ray diffraction analysis of 17g reveals a supramolecular ribbon based on intermolecular hydrogen bonds between two different conformeres of 17g and in addition establishes unequivocally the imid-structures of 9 and 12. Intermolecular cyclisation of 13 with amino-tetrazol 18 gives the azido-pyrrolo-pyrimidine-diones 20, which reacts with triphenylphosphane to give phosphinimines 22. The structure of 22a was established by X-ray diffraction.
Die Reaktion von MoCl4mit TeCl4: Synthese und Struktur von Tris(trichlorotelluronium)hexachloromolybdat(IV)-chlorid,([TeCl3]+)3[MoCl6]2-(Cl-) / The Reaction of MoCl4 with TeCl4: Synthesis and Crystal Structure of Tris(trichlorotelluronium)Hexachloromolybdate(IV)Chloride,([TeCl3]+)3[MoCl6]2-[Cl-]
Authors: Beck J.
Published: February 2015

Red crystals of (TeCl3)3MoCl6(Cl) are obtained by reacting MoCl4 with TeCl4 in a 1:3 molar ratio in a sealed evacuated ampoule at 170°. The crystal structure determination (orthorhombic, space group Cmc21, a = 1541.6(2), b = 1268.1(1), c = 1180.6(1) pm) shows the presence of trigonal-pyramidal [TeCl3]+ ions, octahedral [MoCI6]2- ions, and isolated Cl- ions. The ions are linked by long Te-Cl bridges resulting in distorted TeCl6 octahedra. The octahedra are connected by joint edges and corners to zig-zag chains running along the polar c axis.
Crystal and Molecular Structures of Two Isomers of Phenylglyoxal Bis(amidinohydrazone) [‘Phenylglyoxal Bis(guanylhydrazone)’] Sulphate
Authors: Koskinen Mikko , Mutikainen Ilpo , Elo Hannu
Published: February 2015

The first crystallographic study on an aromatic analogue of the antileukemic agent methylglyoxal bis(amidinohydrazone) (MGBG) is reported. Thus, the crystal and molecular structures of two different geometrical isomers of phenylglyoxal bis(amidinohydrazone) (PhGBG) sulphate were determined by single-crystal X-ray diffraction. Crystals were prepared by recrystallizing PhGBG sulphate using either water or aqueous ethanol (volume ratio ethanol:water 1:4) as the solvent. Depending on the solvent, different types of crystals were obtained although the PhGBG sulphate employed was in the both cases from the same synthesis batch that had been prepared according to classical methods from the corresponding glyoxal. When a crystal obtained from water was studied, PhGBG was found to exist solely in the form of the anti-anti isomer. e. the same isomer that has been observed in the cases of all mono- and dialkylglyoxal bis(amidinohydrazones) so far studied. However, when PhGBG sulphate was recrystallized from 20 % aqueous ethanol, the crystals obtained consisted of a different geometrical isomer. In this anti-syn isomer the carbon-nitrogen double bond closest to the phenyl group had the syn configuration. In the anti-syn isomer, there is an internal hydrogen bond between the two amidinohydrazone moieties, which may markedly contribute to the stabilization of the isomer. The anti-syn isomer of PhGBG is analogous to the only isomer of trifluoromethylglyoxal bis(amidinohydrazone) so far observed. PhGBG sulphate constitutes the first case in which two different geometrical isomers of a bis(amidinohydrazone) have been observed. In the case of the much studied aliphatic mono- and dialkylglyoxal analogues, isomerization of the bis(amidinohydrazone) backbone has never been observed. The structural flexibility of the bis(amidinohydrazone) chain of PhGBG is obviously attributable to the electron-withdrawing resonance effect and perhaps also to the inductive and hyperconjugative effects of the phenyl group. The obviously facile isomerization of PhGBG may markedly influence the biochemical properties of the compound.
Zur Kenntnis des Kupfer-Oxid-Arsenats Cu4O(A sO4)2 / On the Copper Oxide Arsenate Cu4O(AsO4)2
Authors: Staack M. , Müller-Buschbaum Hk.
Published: February 2015

The copper oxide arsenate Cu4O(AsO4)2 has been prepared and investigated by single crystal X-ray techniques. The compound crystallizes with triclinic symmetry, space group C1
i-P1̄, a = 6.4148(7), b = 7.6549(5), c = 8.2241(7) Å, α = 98.52(1), β = 112.39(1), 7 = 98.38(1)°, Z = 2. Cu4O(AsO4)2 is isotypic to Cu4(PO4)2O . Copper ions on one of the four specified sites show nearly planar coordination by O2- and may be assigned to the anionic part of the crystal structure. One of the nine different types of oxygen atoms is coordinated by copper exclusively. The compound is therefore classified as an oxide arsenate.
Strukturelle Unterschiede zwischen Sr2(VO)(AsO4)2 und Ba2(VO)(PO4)2 / Strucural Differences between Sr2(VO)(AsO 4)2 and Ba2(V O)(PO4)2
Authors: Müller-Buschbaum Hk.
Published: February 2015

Two new alkaline earth vanadyl compounds, Sr2(VO)(AsO4)2 (I) and Ba2(VO)(PO4)2 (II), have been prepared by solid state reactions in closed quartz tubes and characterized by single crystal X-ray diffraction methods. Crystal data: (I): monoclinic, C6
2h -I2/a, a = 6.873(2), b = 16.307(4), c = 7.196(2) Å, β = 115.67(2), Z = 4; (II): monoclinic, C3
2-I2, a = 9.471(2), b = 5.443(1), c = 16.972(4) Å, β = 101.65(2), Z = 4. (I) is isotypic to Sr2(VO)V2O8 and Sr2(VO)(PO 4)2. (II) shows significant differences to the strontium compounds as well as to Ba2(VO)(VO4)2. The differences of the crystal chemistry and the similarity of (II) to Ba2(VO)(PO4)2 H2O are discussed.
Ein neues Baumuster für ein heteronukleares 11 - Valenzelektronensystem: gefaltete 1
∞[SnBi]2-Zickzack-Ketten in der Struktur von K2[SnBi] / A Novel Structure Pattern for a Heteronuclear 11 Valence Electron System: Folded 1
∞[SnBi]2- Zigzag Chains in the Structure of K2[SnBi]
Authors: Asbrand Matthias , Eisenmann Brigitte
Published: February 2015

The compound K2[SnBi] was prepared by reaction of stoichiometric amounts of the elements in graphitized quartz ampoules. K2[SnBi] crystallizes in the orthorhombic system, space group Pbcm (No 57), Z = 4, with a = 680,4(3), b = 1339,(4) and c = 649,9(3) pm. The crystal structure of K2[SnBi] is characterized by folded infinite 1
∞[SnBi] zigzag chains of alternating Sn and Bi atoms. The chains are bent at each Bi atom, the Sn atoms are located at the fold of the chain. Apart from the two covalent Sn-Bi bonds, each Sn atom has two additional collinear Sn-Sn contacts in direction of the fold of the chain which in terms of partial bonds can be assigned a bond order of one half. The repeating unit of the chain [Sn2Bi2]4− is strongly related to the isoelectronic butterfly [Si4]6− in Ba3Si4.
1,1-Organoboration of Sterically Hindered Tetra-l-alkynylsilanes and the Crystal Structure of Tetrakis[1-(3,3-dimethyl)butynyl]silane
Authors: Wrackmeyer Bernd , Maisei Heidi E. , Süß Jürgen , Milius Wolfgang
Published: February 2015

Tetra-1-alkynylsilanes, Si(C≡CR1)4 with R1 = tBu (1) and SiMe3 (2) react with triethylborane, Et3B. by intermolecular 1,1-ethyloboration followed by intramolecular 1,1-vinyloboration, to give the substituted siloles 3 and 5 with two R1C≡C groups linked to silicon. The formation of 5 (R1 = SiMe3) requires exactly one equivalent of Et3B, whereas 3 (R1 = tBu) is formed after ≈ 20 d in boiling toluene in the presence of a large excess of Et3B, and the remaining tBu -C ≡ C groups in 3 do not react with Et3B. The 1,1-organoboration of 2 using one equivalent of 9-ethyl-9-borabicyclo[3.3.1]nonane, Et-9-BBN, proceeds similar to the Et3B-reaction, to give mainly the silole derivative 6, in which the bicyclic ring system is enlarged by two carbon atoms. This product is the result of a kinetically controlled reaction. The single crystal X-ray analysis of 1 has been carried out (space group Pnma; a = 990.0(2), b = 1668.0(3), c = 1479.0(3) pm), and its crystal structure is com pared with that of the corresponding tin compound 1 (Sn).
Synthese von Heteroanaloga der Penicillsäure / Synthesis of Hetero Analogues of Penicillic Acid
Authors: Stachel Hans-Dietrich , Schachtner Josef
Published: February 2015

Keywords

Grignard Reaction, Penicillic Acid, Tetramic Acids, Hydroxamic Acids, Thiepin-2,5-dione
NOTIZEN: Darstellung und Kristallstruktur von Rb6Cl4O / Preparation and Crystal Structure of Rb6Cl4O
Authors: Feldmann Claus , Jansen Martin
Published: February 2015

The preparation and crystal structure of Rb6Cl4O (hexagonal, a = 12,621(4), c = 15,847(4) Å) are reported. The compound crystallizes in the anti-K4CdCl6 type of structure, which is closely related to the perovskites. Rb6Cl4O is the first 4:1 compound in pseudo-binary systems MX/M2O (M = alkali metal; X = halide, Au-, CN-, NO2
- ).
The Space Group of MgAl2Se4 and MgIn2Se4
Authors: Range Klaus-Jürgen
Published: February 2015

The correct space group of MgAl2Se4 and MgIn2Se4 is most probably R3̄m and not R3̄m as previously reported.
Elektronentransfer und Kontaktionen-Bildung, 45 [1, 2] Strukturänderungen bei der Einelektronen-Reduktion von Tetraphenylbutatrien zum Radikalanion und bei der Zweifach-Deprotonierung von Tetraphenyl-butin-2 zum Tetraphenylbutatrien-Dianion / Electron Transfer and Contact Ion Pair Formation, 45 [1,2] Structural Changes on Single Electron Reduction of Tetraphenylbutatriene to its Radical Anion and on Twofold Deprotonation of Tetraphenylbutyne-2 to the Tetraphenylbutatriene Dianion
Authors: Bock H. , Arad C. , Näther C. , Göbel I. , John A. , Baur R.
Published: February 2015

Tetraphenylbutatriene is reduced under aprotic conditions to its ESR/ENDOR-spectroscopically characterized radical anion and to its dianion, with both electron transfers quasireversible according to cyclovoltammetric measurements. The alkali cation salts, the red contact ion pair [(H5C6)4C4·⊖][Na⊕ (H3COCH2CH2OCH3)3] and the dark violet contact ion triple [(H5C6)4C4⊖⊖][Li⊕(H3COCH2CH2OCH3)3]2 can be prepared by single electron reduction at a sodium metal mirror or by twofold de-protonation of 1,1,4,4-tetraphenylbutyne-2 using lithium-n-butyl. Their single crystal structures as well as that of the parent acetylene have been determined at low temperatures. The essential structural changes observed are the twisting of both molecular halves (H5C6)2CC relative to each other with increasing negative charge. The simultaneously resulting bond alternancy >C = C = C = C< → >C⊖ - C ≡ C⊖ - C < within the cumulene chain is discussed based on MNDO calculations for the structures determined.
Tetrakis(trimethylphosphaniminato)molybdän-dichlorid, [Mo(NPMe3)4]Cl2 / Tetrakis(trimethylphosphoraneiminato)molybdenum Dichloride, [Mo(NPMe3)4]Cl2
Authors: Rhiel Markus , Wocadlo Sigrid , Massa Werner , Dehnicke Kurt
Published: February 2015

[Mo(NPMe3)4]Cl2 has been prepared by the reaction of MoNCl3 with N-(trimethylsilyl)trimethylphosphanimine in dichloromethane solution from which the complex crystallizes with one CH2Cl2 molecule per formula unit. [Mo(NPMe3)4]Cl2·CH2Cl2: Space group P21/c, Z = 4. Lattice dimensions at-40°C : a = 1244.2( 1), b = 1609.6(1), c = 1595.9( 1) pm, β = 90.36( 1)°. The structure consists of chloride ions and dications [Mo(NPMe3)4]2+ in which the molybdenum atom is tetrahedrally coordinated by the four nitrogen atoms of the (NPMe3)- groups with MoN bond lengths of 180.7 pm in average which correspond with double bonds.
N,N′-Dim ethylharnstoff als chelatisierende Lewis-Säure: Synthese und Kristallstrukturen von PPh4[Cl(H2Me2N2CO)] und (PPh4)2[Cl(H2Me2N2CO)]Cl / N.N′-Dimethylurea as a Chelating Lewis Acid: Synthesis and Crystal Structures of PPh4[Cl(H2Me2N2CO)] and (PPh4)2[Cl(H2Me2N2CO)]Cl
Authors: Ghassemzadeh Mitra , Harms Klaus , Dehnicke Kurt
Published: February 2015

The title compounds have been prepared from tetraphenylphosphonium chloride and N,N′- dimethylurea in acetonitrile using different molar ratios of the educts. Both compounds were characterized by IR spectroscopy and by crystal structure determinations.

PPh4[Cl(H2,Me2,N2,CO)]: Space group P1̅, Z = 4 ,a = 1021.8(2), b = 1192.7(2), c = 2143.9(4) pm, α = 87.21(3)°, β = 85.95(3)°, γ = 74.16(3)° (-50°C).

(PPh4)2[Cl(H2Me2N2CO)]Cl: Space group P21/n, Z = 4, a = 1138.4(2), b = 2855.4(3), c = 1394.0(1) pm, β = 91.19(10)° (-60°C).

In both compounds the N.N′-dimethylurea molecule acts as a chelating Lewis acid via two Cl···H hydrogen bonds forming nearly planar ClH2N2C-six-membered heterocycles.
Synthese und Struktur der Vanadyl-, Cobalt(III)-, Nickel(II)-, Kupfer(II)-, Zink(II)- und PalIadium(II)-Komplexe eines vierzehngliedrigen ungesättigten Tetraazadibenzo-Makrocyclus / Synthesis and Structures of the Vanadyl, Cobalt(III), Nickel(II), Copper(II), Zinc(II) and Palladium(II) Complexes of a 14-Membered Unsaturated Tetraazadibenzo Macrocycle
Authors: Feldhaus Ralf , Köppe Jens , Mattes Rainer , Voet Ulrich
Published: February 2015

The synthesis and structural characterisation of complexes of the 14-membered macrocyclic trans-N4 dibenzo ligand 7,8,9,16,17.18-hexahydrodibenzo[e,l][1,4, 8.11]-tetraazacyclotetradecine (L1) is described. The crystal structures of six compounds were determined by single crystal X-ray diffraction. In [CuL1]2+ the metal atom is tightly bound within the macrocyclic cavity. The Cu-N bonds [201.2(3) and 191.8(3) pm] are rather short. Zn(II) is penta-coordinated in [Zn(L1)Cl]+ with the metal center outside the cavity. L1 is deprotonated at one or both secondary amine functions in the complexes [Ni(L1-H)]+, [Co(L1-2H)]+, [VO(L1-2H)] and [Pd(L1-2H)]. With the exception of [VO(L1-2H)] the metal ions assume nearly square planar N4-coordination, which is very rare for Co(III). Salts of [Co(L1-2H)]+ display a temperature independent magnetic moment of 0,64 B. M. The nickel, cobalt and palladium complexes show remarkably short metal-nitrogen bond distances: Ni-N [183.8(8)], Co-N [181.8(2)] and Pd-N [194.5(6) pm], respectively. The UV/Vis and EPR spectra, and the electrochemical behaviour of some of these complexes are also discussed.
Chemistry of the 1,3,5-Triaza-2-phosphorin-4,6-diones, Part XI*. Base-Catalyzed Addition Reactions of 2-Oxo-2-hydro-1,3,5-trimethyl-1,3,5-triaza-2λ4-phosphorine-4,6-dione to the C=N Double Bond of 3-Thiazoline Heterocycles
Authors: Neda Ion , Kaukorat Thomas , Jones Peter G. , Schmutzler Reinhard , Grögerh Harald , Marte Jürgen
Published: February 2015

The base-catalyzed reaction of 2-oxo-2-hydro-1,3,5-trimethyl-1,3,5-triaza-2λ4-phosphorine- 4,6-dione (1) and of its trimethylsiloxy phosphorus(III) derivative (10) with various 3-thiazolines (2 -5 ) via five different pathways is described. In all cases, the corresponding 3-thiazoline adducts were formed. The different routes are compared with regard to reaction conditions and yields. In the reaction of 1 with 5,5-dimethyl-2-isopropyl-3-thiazoline (3) two diastereomers of 7 were formed, as established by 1H , 13C and 31P NMR spectroscopy. The structures of the products 6 and 8 were confirmed by X-ray analysis; the thiazolidine rings display a twist conformation through the sulfur atom. The molecules are linked via inversion centres by hydrogen bonds of the form N-H···O= C.
The Reaction of 2-Hydro-2-oxo-5,6-benzo-l,3,2λ4-dioxaphosphorin-4-one with Imines and Carbonyl Compounds; Unusual Formation and First X-Ray Crystal Structure Determination of a Benzodioxaphosphepinone Ring System
Authors: Kaukorat Thomas , Neda Ion , Thönnessen Holger , Jones Peter G. , Schmutzler Reinhard
Published: February 2015

On treatment of 2-hydro-2-oxo-5,6-benzo-1,3,2λ4-dioxaphosphorin-4-one (1) with the inline trimers trim ethyl- and tribenzyltriazine and the (monomeric) methylene-tert-butylimine, an insertion reaction of the imine molecule into the P-H bond of 1 took place, forming com pounds 2 -4 . Similar results were obtained when 1 was allowed to react with aldimines, asymmetric at carbon, leading to 5-7 . The diastereotopic properties of 5 - 7 were observed by 1H NMR spectroscopy. NMR and IR spectroscopic investigations on 5 - 7 indicated > C = O···H-N < interactions. Upon reaction of 1 with hexafluoroacetone, trifluoroacetophenone or phenyltrifluoromethylketimine, the derivatives 8 -1 0 , involving a P-O-C fragment, were obtained. The formation of the isomeric “alcohol form ”, bearing a P-C-OH fragment, could not be proved. In the reaction of 1 with various o-quinones. one of the oxygen atom s of the quinone was found to be bonded to phosphorus, whereas the hydrogen atom was found to migrate to the second oxygen atom . Upon reaction of 1 with chloral, an unusual ring expansion took place with formation of the benzodioxaphosphepinone (14). The reaction of 1 with other aldehydes could not be realized. In the reaction of 14 with triethylamine, the ammonium salt 15 was formed. For the first time, an X-ray crystal structure determination of a dioxaphosphepinone ring system was conducted; in 15 the seven-membered ring displays a pseudo tub conformation.
Wechselwirkungen in Kristallen, 89 [1 - 3] Donator/Akzeptor-Komplexe von Alkyl- und Aminobenzolen, Anthracen oder Pyren mit 1,3,5-Cyan-/Nitro-benzolen: Kristallisation, Strukturen und Elektronenspektren / Interactions in Crystals, 89 [ 1 - 3] Donor/Acceptor Complexes of Alkyl and Aminobenzenes, Anthracene or Pyrene and 1,3,5-Cyano/nitro-benzenes: Crystallisation, Structures and Electronic Spectra
Authors: Bock Hans , Ziemer Klaus , Näther Christian , Schödel Holger , Kleine Markus , Sievert Mark
Published: February 2015

The following mixed-stack donor/acceptor complexes {D···A}∞ have been crystallized and their structures determined: {hexamethylbenzene···3,5-dicyano-1-nitrobenzene hexamethylbenzene···3,5-dinitro-1-cyanobenzene}∞, {pyrene···3,5-dinitro-1-cyanobenzene}∞, {anthracene···(3,5-dinitro-1-cyanobenzene)2}∞, {N,N-dimethylanilin···3,5-dinitro- 1-cyanobenzene}∞ and { 1-3-phenylenediamine···3,5-dinitro-1-cyanobenzene}∞. Their lattice packing consists of parallel layers, which contain either donors and acceptors as for hexamethylbenzene and pyrene or composite ones as in the 1:2 complex of anthracene with each one of the acceptors above and below its peripheral rings. The isostructural hexamethylbenzene complexes exhibit almost identical packing coefficients as well as a hexagonal coplanar arrangement of the C6(CH3)6 donors. Weak intermolecular van der Waals interactions are also observed between antiparallel cyano substituents. The interplanar n distances range between 334 and 353 pm, i. e. around 340 pm of two van der Waals n radii. In none of the complexes, however, significant structural changes in either the donor or the acceptor components due to the complex formation are observed. In both the crystals as well as in solution, the donor/acceptor complexes exhibit colours between yellow and red; their long-wavelength charge transfer absorption maxima, therefore, correspond to a lowering in excitation energy of only up to 1 eV relative to that of the components. The different charge transfer in the ground and the CT excited states is also discussed referring to other data such as vertical first ionization energies or interplanar distances {D···A}, as well as to results from semiempirical calculations based on the crystal structure data determined and including approximate configuration interaction.
Darstellung, 19F- und 195Pt-NMR-Spektren, Schwingungsspektren und Normalkoordinatenanalyse von Fluoro-Chloro-Bromo-Platinaten(IV) / Preparation, 19F and 195Pt NMR Spectra, Vibrational Spectra and Normal Coordinate Analysis of Fluoro-Chloro-Bromo-Platinates(IV)
Authors: Drews H.-H. , Preetz W.
Published: February 2015

By stereoselective ligand exchange reactions of [PtF5Cl]2− and cis-[PtF4Cl2]2− with Br− mixtures containing seven different fluoro-chloro-bromo- and two fluoro-bromo-platinates(IV) are formed, from which trans-Cs2[PtF4ClBr] 4t 11 and mer-Cs2[PtF3Clc
2Br] 3m2c 1 have been isolated by ion exchange chromatography on DEAE cellulose. All threefold mixed complexes could be detected by in situ 19F and 195 Pt NMR measurements. Due to the stronger trans influence of Cl in comparison with F on asymmetric F′-Pt-Cl′ axes the F atoms are deshielded and their signals δ(19F) are shifted on the average by 106 ppm to lower field as compared with δ(19F) of symmetric F-Pt-F axes. For the same reason the mean coupling constant 1J(FPt) of 1857 Hz is 44 % higher than 1J( FPt) of 1288 Hz. The substitution of a cis positioned Cl against Br causes shifts of -7,6 ppm for δ(19F) and of -8,4 ppm for δ(19F ). The cis influence on the coupling constants 1J(F P t) and 1J( FPt), on the average 4 Hz, is more than two orders of magnitude smaller than the trans influence. The coupling constants between inequivalent F atoms 2J(FF) amounts to 44 Hz. The mean highfield shift of the l95Pt signals on exchange of one F for Cl is 1177, of one Cl for Br 210 ppm. Due to the increasing trans influence F < Cl < Br on the stretching vibrations of asymmetrically coordinated axes characteristic frequency shifts of up to 15 % are observed. The normal coordinate analyses performed on 4t11 and 3m2c 1 reveal that the force constant fd(PtF) is by 15 % higher than fd(PtF), and that fd(PtCl′) is by 31 % higher than fd(PtCl). Very intense Raman bands at 277 and 267 cm −1 are explained by strong vibrational coupling of the π-deformation with a symmetric valence mode of the Cl -Pt-Br′axis.
Darstellung, Kristallstruktur und physikalische Eigenschaften von Oktasilbertrigermanat, Ag8Ge3O10 / Synthesis, Crystal Structure and Physical Properties o f Octasilver Trigermanate, Ag8Ge3O10)
Authors: Linke Christoph , Jansen Martin
Published: February 2015

Ag8Ge3O10 was obtained from a mixture of the binary oxides by solid state reaction in the presence of a small amount of water which is acting as an accelerator. Conditions applied were T = 500 °C and p(O2) = 1,2 kbar. According to an X-ray crystal structure analysis the title compound contains four crystallographically independent trigermanate [Ge3O10]8− ions per unit cell (Pc, a = 12.1549(11), b = 10.7375(14), c = 18.5169(20) Å, β = 92.326(10)°, 13448 independent reflections, R1 = 6 ,1 %, wR2 = 13,0%, Z = 8). Thermal decomposition, as recorded by DTA and temperature dependent Guinier photographs, occurs at 520 °C. Ag8Ge3O10 is diamagnetic with a molar susceptibility of -330 ·10−6 cm3 mol−1.
Reaktion von Ph3P=C=PPh3 mit Fe(CO)5; Molekülstrukturen von (CO)4Fe=C=C=PPh3 und Fe3(CO)9 (μ3 -η2-C≡C-PPh3) / Reaction of Ph3P=C=PPh3 with Fe(CO)5; Molecular Structures of (CO)4Fe=C=C=PPh3 and Fe3(CO)9(μ3 -η2-C≡C-PPh3)
Authors: Petz Wolfgang , Weller Frank
Published: February 2015

The ylide Ph3P=C=PPh3 reacts with Fe(CO)5 in toluene to give the metallacumulene (CO)4Fe=C=C=PPh3 (1) and O=PPh3. A mixture of the ylide with its hydrolysis product Ph2P(O)-CH=PPh3 produces the trinuclear cluster Fe3(CO)9(μ3-η2-C≡CPPh3) (2) in low yields which can also be obtained from 1 and Fe2(CO)9. Both compounds contain the same ligand bonded in a terminal (1) and in a bridging (2) manner. 1 and 2 crystallize in the monoclinic space groups P2(1)/n and P2(1)/c, respectively, with the unit cell parameters a = 1008.35(10), b = 1167.89(10), c = 1875.10(10) pm, β = 99.824(10)° for 1 and a = 853.6(2), b = 1966.6(4), c = 1770.2(4) pm; β = 99.05(3)° for 2. The compounds are further characterized by IR and NMR (13C ,31P) spectroscopy and elemental analyses.
Synthesis and Characterization of Aza-Trimetalla Tetrahedranes
Authors: Herberhold Max , Bertholdt Uwe , Wrackmeyer Bernd
Published: February 2015

The sulfimide complex Fe2(CO)6(μ-SNH) (1) reacts with Co2(CO)8 to form a 1:1 mixture of the known clusters FeCo2(CO)9(μ3-S) (2) and FeCo2(CO)9(μ3-NH) (3). The azatetrahedrane 3 may be used as a precursor for the synthesis of the new aza-trimetalla tetrahedranes Fe2Co(CO)9(μ-H)(μ3-NH) (5), CpMoFeCo(CO)8(μ3-NH) (6), CpNiFeCo(CO)6(μ3-NH) (7) and (CpNi)2Fe(CO)3(μ3-NH) (8) which were obtained from exchange reactions of 3 with Na2[Fe(CO)4], Na[CpMo(CO)3] and [CpNi(CO)]2. However, the reactions of 3 with Na2[Fe(CO)4] and Fe3(CO)12 gave Fe3(CO)9(μ-H)2(μ3-NH) (9) only as a minor product in addition to large amounts of Fe3(CO)9(μ-H)2(μ3-S) (10). The 1H NMR spectra of 3 and 5 - 9 show a broadened triplet for the NH proton between δ(1H) 8.21 and 9.53. Chemical shifts δ(14N) were determined most efficiently by heteronuclear 1H {14N} double resonance experiments. The δ(14N) values for aza-trimetalla tetrahedranes (-180 to -202) indicate delocalized bonding between the μ3-bridging nitrogen atom and the metal triangle.
Notizen: On the Structure of t-Butylaminotriphenylphosphonium Iodine Dichloride
Authors: Amer Adel , Mayer Andrea , Ho Douglas , Zimmer Hans
Published: February 2015

The structures of t-butylaminotriphenylphosphonium iodine dibromide and iodine dichloride were determined by Raman spectroscopy and Xray crystallographic structure analysis. The iodine dibromide [IBr2]− species was assigned a centrosymmetric nature, whereas the iodine dichloride [ICl2]− possesses a non-centrosymmetric structure.
Reaction of Borane in Tetrahydrofuran with 1,1,3,3-Tetramethyldisilazane and Cyclic Disilazanes - Competition Between N-Si and N-H Bond Cleavage
Authors: Wrackmeyer Bernd , Schwarze Bernd
Published: February 2015

Borane in tetrahydrofuran (THF-BH3/THF; 1) reacts with 1,1,3,3-tetramethyldisilazane (2a) and the cyclic disilazanes

(2b), 3 (2c), 4 (2d)] first by formation of amine-borane adducts (3a - d), and then to give /μ-aminodiboranes(6) by H2 elimination (4a -,d) or cleavage of N-Si bonds (5a-d ), depending on the reaction conditions, in agreement with the results obtained for the reaction of 1 with hexamethyldisilazane. Further transformations proceed via the N,N-disilylaminoboranes 6a - d. In the case of the reaction between 1 and 2b, it proved possible to convert 4b and/or 5b quantitatively into the mixed diaminoborane 7b which served for the synthesis of N,N′,N″-tris[(2′-dimethylsilylethyl)dimethylsilyl]borazine (8b). The Si-H functions in 5b, 7b and 8b react with Co2(CO)8 to afford the respective Si-Co(CO)4 derivatives 11b - 13b. All compounds were characterized by their 1H , 11B, 13C, 14/15N and 29Si NMR spectra.
On the Preparation of 5-(α-DiazoethyI)tetrazoles
Authors: Moderhack Dietrich , Beißner Andreas
Published: February 2015

Hydrazone dehydrogenation with silver(I) oxide in the presence of sodium hydroxide was found an efficient approach to the title compounds, whereas application of the Bamford-Stevens reaction proved unsatisfactory.
Die Kristallstrukturen des Diphenylphosphinsäureamids, Ph2P(O)NH2, und seines Cäsiumsalzes [Cs{Ph2P(O)NH}] / Crystal Structures of Diphenylphosphinic Acid Amide, Ph2P(O)NH2, and of its Cesium Salt [Cs{Ph2P(O)NH}]
Authors: Schlecht Sabine , Chitsaz Soheila , Neumüller Bernhard , Dehnicke Kurt
Published: February 2015

The crystal structures of the monoclinic form of Ph2P(O)NH2 and of its cesium salt, [Cs{Ph2P(O)NH}] have been determined by X-ray methods.

Ph2P(O)NH2: Space group P21/c, Z = 16, lattice dimensions (-80°C): a = 2530.2(3), b = 858.9(2), c = 2135.5(3) pm, β = 110.78(1)°, R , = 0.055. Diphenylphosphinic acid amide forms dimeric molecules via N-H ··· O hydrogen bonds, the dimeric units again are associated via hydrogen bonds to form infinite double chains along the crystallographic c axis.

[Cs{Ph2P(O)NH}]: Space group Pccn, Z = 8 , lattice dimensions (-83°C): a = 1262.8(1), b = 2632.3(2), c = 769.1(1) pm , R1 = 0.024. The compound is associated via Cs-O and Cs-N contacts along the crystallographic [001] axis forming a tubular arrangement. There are no hydrogen bonds.
Reaktivität nitrophenylsubstituierter cyclischer Amine bei Dehydrierungen / The Reactivity of Nitrophenyl Substituted Cyclic Amines with Dehydrogenations
Authors: Möhrle H. , Mehrens J.
Published: February 2015

Piperidine and perhydroazepine bearing a 1 -(4-nitrophenyl) substituent were inert to mercury-edta, while the a-pipecoline derivative gave an aminoketone with cleavage of the heterocycle. However the corresponding (2-nitrophenyl) compounds reacted to give respectively a piperidin-2-one, an aminopentanal and an aminohexanone.

By an additional substituent in 2′-position the p-nitro compounds underwent dehydrogenation too. With a methyl group resulted a pattern analogous to o-nitro products. A neighbouring hydroxymethyl function enhanced the reaction with formation of benzoxazines and if possible their further oxidized derivatives, the hydroxylactams.
Zur Kristallchemie von Telluraten mit Mn2+ im kationischen und anionischen Teil der Kristallstruktur: (Mn2,4Cu0,6)TeO6, Ba2MnTeO6 und Pb(Mn0,5Te0,5 )O3 / On the Crystal Chemistry of Tellurates Containing Mn2+ in the Cationic and Anionic Part of the Crystal Structure: (Mn2,4Cu0,6)TeO6, Ba2MnTeO6 and Pb(Mn0,5Te0,5)O3
Authors: Wulff L. , Wedel B. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of (Mn2.4Cu0.6)TeO6 (I), Ba2MnTeO6 (II) and Pb(Mn0.5Te0.5)O3 (III) have been prepared by crystallization from fluxes. X-ray investigations led to rhombohedric symmetry (I): R3̄, (II): R3̄m with the trigonal lattice constants (I): a = 8.826(1), c = 10.687(2) Å, Z = 2. (II): a = 5.817(8), c = 14.244(3) Å, Z = 3. Compound (III) crystallizes with cubic symmetry P43̄m, a = 4.045(3) Å, Z = 1. (I) is the first example of a manganese(II) tellurate and belongs to the structure type of A3XO6 compounds like (Mn2In)SbO6, Mn3WO6 and Ca3UO6. (II) exemplifies an ordered and (III) a disordered variation of the perovskites.
Unusual Bonding in Ternary Nitrides: Preparation, Structure and Properties of Ce2MnN3.
Authors: Niewa Rainer , Vajenine Grigori V. , DiSalvo Francis J. , Luob Haihua , Yelon William B.
Published: February 2015

Ce2MnN3 was prepared by reaction of cerium nitride and manganese with nitrogen gas at 900 °C. It crystallizes isotypic to AC2MN3 (Ac = U, Th; M = Cr, Mn) and Ce2CrN3, space group Immm (No. 71), a = 3.74994(6) Å, b = 3.44450(6) Å and c = 12.4601(2) Å. The manganese atoms are coordinated in a nearly square planar fashion by four nitrogen atoms. These corner-connected MnN4 units form infinite 1
∞[MnN2N2/2] chains, which run parallel to each other along the crystallographic a-axis, forming the motif of hexagonal rod packing. Cerium atoms connect the chains into a three-dimensional network. The results of measurements of the magnetic susceptibility, as well as of the electrical resistivity suggest metallic behavior. Electronic effects leading to shorter bonds between manganese and bridging nitrogen atoms than between manganese and terminal nitrogen atoms in the 1
∞[MnN2N2/2] chains were investigated through extended Hückel and LMTO band structure calculations. Issues pertaining to stability of this and some other nitridometallate structures are discussed.
RbAsF6, CsAsF6 und RbSbF6: Kristallstrukturen, Thermische Phasenumwandlungen und Schwingungsspektren / RbAsF6, CsAsF6 and RbSbF6: Crystal Structures, Thermal Phase Transitions, and Vibrational Spectra
Authors: Röhr Caroline , Loss Sandra
Published: February 2015

The title compounds are isostructural to CsSbF6 and crystallize with the KOsF6 structure type (space group RS, Z = 3) with the lattice constants a = 749.7(1) pm, c = 758.9(1) pm (RbAsF6), a = 772.3(1) pm, c = 805.0(1) pm (CsAsF6) and a = 767.0(1) pm, c = 786.1(2) pm (RbSbF6). The structures exibit nearly ideal [MF6]– octahedra, the alkaline cations are coordinated by 12 fluorine ions in a distorted cuboctahedral geometry. Cations and complex anions form a slightly distorted CsCl arrangement. On heating, the arsenates transform to a NaCl arrangement with disordered [AsF6] ions, whereas the antimonates of Rb and Cs form the corresponding disordered CsCl type at higher temperatures. The phase transitions and the i. r. and Raman spectra as well as the structural relations to the remaining hexafluoropnictates AI[MVF6] are discussed.
Untersuchungen an Polyhalogeniden, XXXIII [1] Polyiodide des Nickelhexamminkomplexes: Nickelhexamminbistriiodid [Ni(NH3)6](I3) 2 und Nickelhexamminbispentaiodid [Ni(NH3)6](I5)2 / Studies of Polyhalides, 33 [11 Polyiodides of the Nickel Hexammine Complex: Nickelhexammine Bistriiodide [Ni(NH3)6](I3) 2 and Nickelhexammine Bispentaiodide [Ni(NH3)6](I5)2
Authors: Tebbe Karl-Friedrich , Gilles Theo , Radke Bernhard
Published: February 2015

The compounds [Ni(NH3)6](I3)2 and [Ni(NH3)6](I5)2 have been prepared by the reaction of stoichiometric amounts of [Ni(NH3)6]Cl2, KI, and I2 in water. The already known triiodide crystallizes in the monoclinic space group C2/c with a = 1541,0( 10), b = 1521.6(8), c = 876.1 (7) pm, β = 101.44(6)° and Z = 4. The new pentaiodide crystallizes in the monoclinic space group P21/n with a = 899.6(4), b = 1681.6(5), c = 946.8(7) pm, β = 110.90(5)° and Z = 2. Both compounds contain nearly octahedral cations [Ni(NH3)6]2+ and simultaneously a linear and a bent triiodide ion I3
- with nearly equal bond lengths or a unsymmetrical V-shaped pentaiodide ion I5
- which is lined up to a new type of pentaiodide chain.
Übergangsmetallkomplexe mit Nitroxidradikalen: Palladium-, Platin-, Pentamethylcyclopentadienyl-rhodium- und -iridium-Komplexe sowie α-Aminocarboxylatkomplexe mit Donor-haltigen Derivaten des 2,5-Dihydroimidazol-l-oxyls / Transition Metal Complexes of Nitroxide Radicals, Palladium, Platinum, Pentamethylcyclopentadienyl Rhodium and Iridium Complexes, and α-Aminocarboxylate Complexes with Derivatives of 2,5-Dihydroimidazole-l-oxyls
Authors: Hintermaier Frank , Helding Sylvia , Volodarsky Leonid B. , Sünkel Karlheinz , Polbom Kurt , Beck Wolfgang
Published: February 2015

2,5-Dihydroimidazoline-l-oxyl radicals I, II with imino substituents coordinate to Pd(II) and Pt(II) complexes with formation of the N,N chelate complexes 1-6. With oxygen containing substituents either monodentate N-coordination to give 8 or N ,O chelate formation to give 9 takes place, depending on the position of the oxygen atom relative to the ring nitrogen atom. With radicals III that also have the second ring nitrogen atom oxidized and the Rh(III) or Ir(III) complexes [Cp*MCl2]2 the O , O chelates 11 -13 could be obtained, while with Na2PdCl4 the heterocycle was destroyed with formation of a N,N chelate complex 10 of an α-nitrosooxime ligand. The orthopalladated 2,2,5,5 tetramethyl-4-phenyl-2,5-dihydroimidazoline-l-oxyl complex 7a reacts with several a-amino acidates under splitting of the dichloro bridge with formation of the C,N/N,O-bis-chelate complexes 7b-f. The molecular structures of 2 and 10 were determined by X-ray diffraction.
Zum System Sr/Mo/O: Phasendiagramm, Synthese und Charakterisierung der ternären Verbindungen / On the System Sr/Mo/O: Phase Diagram, Synthesis and Characterization of Ternary Compounds
Authors: Steiner U. , Reichelt W.
Published: February 2015

The phase diagram of the ternary system Sr/Mo/O has been determined at a temperature of 1000°C. Powder samples of the ternary compounds SrMoO4, Sr3MoO6, SrMoO3, Sr2MoO4 and SrMo5O8 were prepared by solid state reactions. The thermochemical data of all ternary compounds were determined. A new compound, Sr3Mo2O7, with a layered perovskite structure (a = 3.967(1), c = 20.588(5) Å, I4/mmm) was found. Rietveld analysis based on powder X-ray diffraction data confirms that the compound Sr2MoO4 has the K2NiF4 structure (I4/mmm) with a = 3.9176(1), c = 12.8545(4) Å.
Enantioselective Catalysis, 122 [1] Synthesis of New Optically Active 3,5-DinitrosalicyloxazoIines
Authors: Brunner Henri , Haßler Bernd
Published: February 2015

New optically active 3,5-dinitrosalicyloxazolines, derived from 3,5-dinitrosalicylonitrile and the chiral aminodiols (1S,2S)-(+)-2-amino-1-phenyl- 1,3-propanediol, (2S)-(-)-2-amino-1,1,4,4-tetraphenyl- 1,4-butanediol and (2S)-(-)-2-aminol, 1-diphenyl-1,3-butanediol, were prepared and used as in situ catalysts for enantioselective cyclopropanation reactions.
Oligomere Tetraeder-Anionen in Borophosphaten: Darstellung und Kristall­strukturen von NaFe[BP2O7(OH)3] und K2Fe2[B2P4O16(OH)2 ]/Oligomeric Tetrahedral Anions in Borophosphates: Synthesis and Crystal Structures of NaFe[BP2O7(OH)3] and K2Fe2[B2P4O16(OH)2]
Authors: Boy Insan , Cordier Gerhard , Eisenmann Brigitte , Kniep Rüdiger
Published: February 2015

Crystals of the title compounds were grown under hydrothermal conditions. The crystal structures were determined by single crystal data.

NaFe[BP2O7(OH)3] (monoclinic, C 2/c, a = 1042.0(2), b = 821.5(1), c = 921.7(1) pm, β = 116.60(1)°, Z=4): The crystal structure contains isolated anions [BP2O7(OH)3]4-, which correspond to trinuclear units PO1/2O3-BO2/2(OH)2 -PO1/2O2(OH) of corner sharing tetrahedra. Fe3+ is coordinated octahedrally by oxygen, Na+ is 8 -fold coordinated by oxygen forming cubes.

K2Fe2[B2P4O16(OH)2] (triclinic, P1̄, a = 516.7(1), b = 808.9(1), c = 834.0(1) pm, α = 87.06(f), β = 80.21(1), γ = 86.59(1)°, Z = 1): The crystal structure contains isolated anions [B2P4O16(OH)2]8-. Four-membered rings of tetrahedra with two additional terminal phosphate groups are formed by condensation of two trinuclear units P O1/2O3 -BO3/2(OH) -PO2/2O2. Fe3+ is in an octahedral and K+ in an irregularly 10-fold coordination by oxygen.
(Triphenylarsine)gold(I) Complexes: Synthesis of an Oxonium Salt and Redistribution of the Arsine Ligands
Authors: Tripathi Upendra M. , Schier Annette , Schmidbaur Hubert
Published: February 2015

The reaction of [(Ph3As)AuCl] with Ag2O in the presence of NaBF4 in tetrahydrofuran affords three products, identified as [(Ph3As)4Au]BF4 (40.3%), [(Ph3As)2Au]BF4 (16.4%) and {[(Ph3As)Au]3O}BF4 (17.3%). The properties of the main product agree well with recent literature data. The other two compounds are new and have been identified by their analytical, spectroscopic, and crystallographic data. The structures are isomorphous with those of the analogous Ph3P complexes. Variations in the stabilities are discussed in terms of kinetic and thermodynamic effects.
Thermische Zersetzung und Lösungskalorimetrie von Ammoniumneodymchloriden/Thermal Decomposition and Solution Calorimetry of Ammonium Neodymium Chlorides
Authors: Hennig C. , Oppermann H.
Published: February 2015

The thermodynamical data of ammonium neodymium chlorides (NH4)2NdCl5 and NH4Nd2Cl7 were derived by the determination of their decomposition equilibria by total pres­sure measurements. Moreover, solution calorimetry was applied. The enthalpies of formation of these phases were calculated from their heats of solution and from the enthalpies of formation and the heats of solution of NdCl3 and NH4Cl.

Data by total pressure measurement:

ΔH°B((NH4)2NdCl5,f,298) = - 412,5 ± 3,6 kcal/mol;

S°((NH4)2NdCl5 f 298) = 80,1 ± 5,8 cal/K · mol;

ΔH°B(NH4Nd2Cl7,f,298) = -579,5 ± 3,5 kcal/mol;

S°(NH4Nd2Cl7,f,298) 101,8 ± 5,6 cal/K mol.

Data by solution calorimetry:

ΔH°B(NdCl3,f,298) = -251,2 ± 0,7 kcal/mol;

ΔH°B((NH4)2NdCl5,f,298) = -405,5 ± 1,0 kcal/mol;

ΔH°B(NH4Nd2Cl7,f, 298) = -576,8 ± 1,7 kcal/mol.
Photoreactivity of Titanocene Pentasulfide
Authors: Kunkely Horst , Vogler Arnd
Published: February 2015

The electronic spectrum of Cp2TiS5 shows a long-wavelength absorption at λ max = 492 nm which is assigned to the lowest-energy S5
2- → TiIV ligand-to-metal charge transfer (LMCT) transition. The photolysis of the complex in CH2CI2 leads to the formation of Cp2TiCl2 and elemental sulfur. It is suggested that LMCT excitation initiates a reductive elimination with the extrusion of S5 while the reduced titanocene is reoxidized by the solvent.
18-Krone-6 und kleine Carbonsäuren. Bildung und Struktur binärer Addukte mit Ameisen-und Essigsäure sowie ternärer mit Essigsäure und Wasser/18-Crown-6 and Small Carboxylic Acids. Formation and Structure of Binary Adducts with Formic and Acetic Acid, as well as Ternary Ones with Acetic Acid and Water
Authors: Albert Antje , Mootz Dietrich
Published: February 2015

The melting diagrams of the binary systems 18-crown-6/formic acid and 18-crown-6/acetic acid have been set up and the crystal structures of the adducts 18C6 · 2 HCOOH (1, space group P 21/c with Z = 2 formula units per unit cell) and 18C6 · 2 CH3COOH (2, C2/m, Z = 2) determined. Furthermore three ternary phases, 18C6 · CH3COOH · H2O (3, P21/c, Z = 4) and dimorphic 18C6 · 2 CH3COOH · 4 H2O (high temperature form 4, P21/n, Z = 2; low temperature form 5, P21/n, Z = 2) have been characterized in the same way. In each structure the crown ether molecule has the (pseudo) D3d conformation common for many of its complexes. Various aspects of the intermolecular hydrogen bonding are described.
Redoxreaktionen von Molybdänverbindungen mit Bis(2-salicyliden- aniinophenvl Klisulfid. Kristallstruktur von Salicylaldehyd-2-mercapto- anilato(2-)-triphenylphosphanoxid-dioxomolybdän(VI) Redox / Reactions of Molybdenum Compounds with Bis(2-salicylidene-aminophenyl)disulfide. Crystal Structure of Salicylaldehyde-2-mercaptoanilato(2-)– triphenylphosphaneoxide-dioxo- molybdenum(VI)
Authors: Banße Wolfgang , Fliegner Jana , Sawusch Stefan , Schilde Uwe , Uhlemann Erhard
Published: February 2015

The reactions of Mo(CO)6, Mo(acac)2(NO)2, and MoO2(acac)2 with bis(2-salicylideneaminophenyl) disulfide in the presence of triphenylphosphane have been studied. The crystal structure of salicylaldehyde-2-mercaptoanilato(2-)-triphenylphosphaneoxidedioxomolybdenum (VI) was determined by X-ray analysis.
Ag+ als Substituent eines Alkalimetalls in Ag2SrMnV2O8 / Ag+ As Substituent Of An Alkaline Metal In Ag2SrMnV2O8
Authors: Rettich R. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of Ag2 SrMnV2O8 have been prepared by reactions of metallic silver and a mixture of SrCO3, MnCO3 · H2O and V2O5. X-Ray investigations showed monoclinic symmetry, space group C6
2h -C2/c, a = 9.7022(9), b = 5.5882(5), c = 13.894(1), β = 90.41(1)°, Z = 4. The crystal structure is isotypic to Na2BaCuV2O8 and includes VO4 tetrahedra, MnO6 octahedra as well as irregular AgO8 and SrO10 polyhedra. Ag2SrMnV2O8 is characterized by a [MnV2O8] network incorporating Ag+ and Sr2+ or a [Ag2V28] frame incorporating Mn2+ and Sr2+ ions. Ag+ is able to replace an alkali ion in the cationic part of the crystal structure.