bluuebunny/crossref_metadata_2025 huggingface dataset:
Kristallstruktur von Tribromosulfonium(IV)-hexafluoroantimonat(V) SBr3
+SbF6
- [1] / Crystal Structure of Tribromosulfonium(IV)-hexafluoroantimonate(V) SBr3
+SbF6
- [1]
Authors: Minkwitz R. , Lekies R. , Preut H.
Published: March 2015

The crystal structure of SBr3
+SbF6
-is reported. It shows short contacts between the S atom of the cation and F atoms of surrounding SbF6
-anions such that a distorted ψ-octahedral coordination around S is formed. Besides these short S···F-distances, there are short Br···F-contacts in the crystal and nine- and ten-membered heterocycles are formed via S -Br- and Sb-F-bonds and Br···F-contacts.
Von lithiierten Aminofluorsilanen zu mono- und dimeren Iminosilanen / From Lithiated Aminofluorosilanes to Mono- and Dimeric Iminosilanes
Authors: Stalke Dietmar , Keweloh Nayla , Klingebiel Uwe , Noltemeyer Matthias , Sheldrick George M.
Published: March 2015

Depending on the solvent and the bulkiness of the substituents, Iithiated aminofluorosilanes are dimers, monomers, or LiF-adducts of iminosilanes. In the crystal structure of the dimeric lithium derivative of di-tert-butyl(rm-butylamino)fluorosilane, each lithium atom is coordinated by one fluorine and two nitrogen atoms. LiF-elimination leads - if sterically possible - to dimerisation. The limits of dimerisation are reached with the dimer diisopropyl(tri-tert-butylphenyI- imino)silane, for which the crystal structure analysis shows severe steric distortions. Fluorine- chlorine-cxchange occurs in reactions of lithiated (tri-tert-butylphenylimino)fluorosilanes with Me3SiCl. Iminosilanes are obtained by thermal LiCl-elimination from the resulting salts.
Synthese und Kristallstruktur eines Lithium(trimethylacetoxy-di-tert-butylsilanolats) / Synthesis and Crystal Structure of a Lithium(trimethylacetoxy-di-tert-butylsilanolate)
Authors: Dippel Kerstin , Keweloh Nayla K. , Jones Peter G. , Klingebiel Uwe , Schmidt Dieter
Published: March 2015

In an acid medium di-tert-butylsilanediol reacts with acyl chlorides to give the di-tert-butylchlorosilanol (2) and the carboxylic acid. A lithium salt of a silanol-carboxylic acid ester (5) is formed in the reaction of the lithiated diol with 2,2-dimethylpropionyl chloride. 5 reacts with phenylacetyl chloride to give the first mixed dicarboxyl-silane. The crystal structure determination of 5 shows a Li-O-cubane with C = 0 ···Li chelate bonds.
Übergangsmetallkomplexe mit Schwefelliganden, XXXII*: Synthese der sterisch anspruchsvollen Thiolat-amin-Liganden tbu2-ma-H = 2-Mercapto-3,5-di-tbutylanilin und tbu4-bmae-H2 = 1,2-Bis(2-mercapto-3,5-di-tbutylaniIino)ethan sowie ihrer Eisen-, Ruthenium- und Zink-Komplexe [Fe(CO)2(tbu2-ma)2], [Zn(tbu2-ma)2] und [RuL2(tbu4-bmae)], L = CO, PMe3, PPh3/ Transition Metal Complexes with Sulfur Ligands, XXXII*: Synthesis of the Sterically Demanding New Thiolate-amine Ligands tbu2-ma-H = 2-Mercapto-3,5-di-tbutylanilin und tbu4-bmae-H2 = 1,2-Bis(2-mercapto-3,5-di-tbutylaniIino)ethane as well as of their Iron-, Ruthenium- and Zinc Complexes [Fe(CO)2(tbu2-ma)2], [Zn(tbu2-ma)2] and [RuL2(tbu4-bmae)], L = CO, PMe3, PPh3
Authors: Sellmann Dieter , Käppler Olaf
Published: March 2015

In order to obtain soluble complexes containing sterically protected metal centers the new bi- and tetradentate thiolate amine ligands 2-mercapto-3,5-di-tbutylaniline (= tbu2-ma-H) and 1,2-bis(2-mercapto-3,5-di-tbutylanilino)ethane (= tbu4-mae-H2) were synthesized. tbu2-ma-H reacts with FeCl2-4 H2O and CO to give [Fe(CO)2(tbu2-ma)2], with Zn(ac)2 -2 H2O [Zn(tbu2-ma)2] is obtained whose acid hydrolysis and reaction with H2S, respectively, yield pure tbu2-Ina-H. The condensation of tbu2-ma-H with glyoxal yields the respective bis-benzthiazolidine, which is re­duced by LiAlH4 in the presence of Na[N(SiMe3)2] to tbu4-bmae-H2. tbu4-bmae-Li2. reacts with [Ru(CO)3(THF)Cl2], [Ru(PMe3)4Cl2] and [Ru(PPh3)2(CH3CN)2Cl2], respectively, to yield [Ru(L)2(Tm4-bmae)j (L = CO, PMe3, PPh3). The complexes are more soluble in organic solvents than the corresponding unsubstituted bmae complexes, bmae2- = 1,2-bis(2-mercaptoanilino)- ethane(2-).
Ionic Conductivity, Structural, IR and Raman Spectroscopic Data of Olivine, Sr2PbO4, and Na2CuF4 Type Lithium and Sodium Chlorides Li2ZnCl4 and Na2MCl4 (M = Mg, Ti, Cr, Mn, Co, Zn, Cd)
Authors: Lutz Heinz Dieter , Wussow Klaus , Kuske Peter
Published: March 2015

The ionic conductivities (complex impedance measurements) of the olivine type Li2ZnCl4, Na2ZnCl4 and Na2CoCl4, the Sr2PbO4 type Na2MgCl4, Na2MnCl4, and Na2CdCl4, and the novel Na2CrCl4 with monoclinically distorted Sr2PbO4 structure (Na2CuF4 type) are presented. The specific conductivities of Li2ZnCl4 and the Na2MCl4 are about three orders of magnitude lower than those of the fast ionic conducting lithium chloride spinels Li[LiM ]Cl4 (M = Mg, Mn. Fe. Cd. etc.) indicating that in the latter compounds the tetrahedrally coordinated lithium ions exhibit higher mobility than those on octahedral sites. The X-ray data including those of Sr2PbO4 type Na2TiCl4 and both the IR and Raman spectra (together with a group theoretical treatment) are also given. The spectra obtained confirm the different structure types of the ternary chlorides.
Metallcarbonyl-Komplexe mit Anionen von cyclischen Imiden / Metal Carbonyl Complexes with Anions of Cyclic Imides
Authors: Schier Ernst-Jürgen , Sacher Wolfgang , Beck Wolfgang
Published: March 2015

A large series of metal carbonyl complexes with N -bonded anions of various cyclic imidates (X-) has been prepared: [M(CO)5X]-, [M(CO)4(PPh3)X], [M(CO)3(en)X]- (M = Cr, Mo, W), Re(CO)5X , [π-CH3C5H4Mn(CO)2X]-, [Mn(CO)4X2]-. Also pyromellitdiimidate and cyclopentanebis(dicarboximidate) bridged complexes [(OC)5MXM(CO)5]2- (M = Cr, Mo, W) and the dicyanamide complex [π-(C5H5)Mn(CO)2NCNCN]- have been obtained. Reactions at the coordinated imidate ligands and the spectroscopic data of the complexes are reported.
In vitro Study of 137Cs Sorption by Hexacyanoferrates(II)
Authors: Nielsen Peter , Dresow Bernd , Heinrich Hellmuth C.
Published: March 2015

We synthesized a varicty of colloidal and non-colloidal mixed hexacyanoferrate(II) complexes of Fe. Cu. Co. Ni. Zn. Mn and studied ihe cesium Sorption in vitro under physiological conditions (artificial gastric juice. pH 1.2 and artificial duodenal juice. pH 6.8). All of the hexaeyanoferrates under study (except cesium iron(III) hexaeyanoferrate CsFeHCF) sorb tracer amounls of 13 Cs quantitatively. Differences in the sorption capacity become obvious by offering substantial amounts of cesium. Potassium copper hexacyanoferrate(II) (KCuHCF) and potassium zinc hexa- cyanoferrate(II) (KZnHCF) are most efficient in cesium sorption at pH 1.2 and at pH 6.8. The sorption capacities of KCuHCF and KZnHCF (2.3-3.0 mmol Cs'g HCF) are twice as high as for coiloidai Prussian blue (KFeHCF; 1.0-1.3 mmol Cs/g HCF) and insoluble Prussian blue (FeHCF: 1.0-1.6 mmol Cs/g HCF). The most promising Compounds. KCuHCF and KZnHCF. should be further investigated in in vivo studies for 137 |l4cesium decorporation. Evidence indicate that the sorption mechanism for most of the Compounds under study is a cesium/potassium ion-exehange reaction. In the case of insoluble Prussian blue (FeHCF). a cesium/proton exchange was observed. ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ On laboratory scale. 137 |V4Cs-contaminated whey dry powder. produced from South German cow milk in summer 1986 was almost completely decontaminated by dialysing a whey Suspension against buffer Solution containing FeHCF. The 117 "JCs'-ions. completely bound by FeHCF. can be isolatcd from the buffer Solution by simple filtration. The buffer Solution and the FeHCF can
The Temperature-Variable Geometry of the Pseudo-Octahedral CuO6 Entity in Bis(methoxyacetato) diaquo-Cooper(II) - a Single Crystal EPR Study
Authors: Jakob Bernd , Reinen Dirk
Published: March 2015

The Cu-O bond lengths in the pseudooctahedral bis(methoxvacetato)diaquo-copper(II) com­plex are determined by the Jahn-Teller effect on the one hand and by the bonding properties of the three different oxygen ligator atoms (from a carboxylate. water and ether group) on the other. It is derived from EPR single crystal and powder investigations between 4.2 and 350 K. that the system becomes fluxional above =120 K due to a continuous transition from a static to a (par­tially) dynamic Jahn-Teller distortion. A model is presented, which allows to correlate the EPR results with the Cu-O spacings. if they are calibrated with structural data at two different temperatures. The structure of the ground state potential surface of Cu2+ is derived from the spectroscopic data.
Pentamethylcyclopentadienyl-Vanadium Complexes Containing Halogeno- and Oxo-Ligands
Authors: Herberhold Max , Kremnitz Walter , Kuhnlein Markus , Ziegler Manfred L. , Brunn Karl
Published: March 2015

A simple and high-yield preparation of the pentamethylcyclopentadienyl vanadium(IV) trihalides Cp*VX3 (X = CL, Br, I) from Cp*V(CO)4 as well as their conversion into the oxo-vanadium(V) compounds Cp*VOX2 (X = CL, Br) and [Cp*VOX]2(μ-O) (X = CL, Br, I) are described. The equilibrium between the two fluoride species Cp*VOF2 and [Cp*VOF]2(μ-O) has also been investigated. The complexes are characterized by their NMR (51V, l3C, 1H), IR, and mass spectra. The crystal structure of the binuclear chloro-oxo complex [Cp*VOCl]2(μ-O) has been determined by X-ray diffraction. The molecules contain two [Cp*VOCl] units combined via a bent oxo bridge (V-O-V angle of 142.2(2)°). The vanadium-oxygen bond lengths are 157.6(8) and 179.4(1) pm for the terminal and the bridging oxo ligands, respectively, corresponding to double and single bonds.
Synthese und spektroskopische Charakterisierung mehrfach silylierter Ethene / Synthesis and Spectroscopic Characterization of Di- and Trisilylethenes
Authors: Schmidbaur H. , Ebenhöch J.
Published: March 2015

Di- and trisilylethenes have been prepared by catalytic hydrosilylation of trimethylsilyl-, bis-(trimethylsilyl)- and bis(trichlorosilyl)ethyne and converted into the hydrogenated derivatives by LiAlH4-reduction. The stereochemistry of the products and the effects of substitution of methyl vs. chlorine ligands on the NMR coupling constants J(29Si/1H) have been investigated by analysis of selectively (Me)-decoupled 29Si NMR spectra. From the results it has been concluded, that the catalytic hydrosilylation of silylated ethynes proceeds in a stereospecific syn fashion yielding trans adducts. Substitution of methyl by chlorine at one or two Si-atoms in tris(trimethylsilyl)ethene leads to an increase of the coupling constant J(29Si/1H vinyl) with the chlorinated Si-atoms and reduces the values for those Si-atoms, where the methyl groups are retained.
Monomerie Metaphosphate: Does it Exist in Aqueous Solution?
Authors: Keesee R. G. , Castleman A. W.
Published: March 2015

Enthalpy changes for the successive addition of the first four water molecules onto monomeric metaphosphate anion in the gas phase have been determined to be -12.6, -11.4, -16.3, and - 11.0 kcal/mol, respectively. The results suggest that the first addition is a simple formation of the adduct PO3
- · H2O as apposed to formation of the dihydrogen orthophosphate anion (HO)2PO2
-, but that the third addition involves a transformation to the orthophosphate anion.
N-TrimethylsilyMminotriphenylphosphoran-Kupfer(II)-chlorid, [Me3 SiNPPh3 · CuCl 2 ]2 Synthese und Kristallstruktur / N-Trimethylsilyl-iminotriphenylphosphorane Copper(II) Chloride, [Me3 SiNPPh3 · CuCl 2] 2 Synthesis and Crystal Structure
Authors: Fenske Dieter , Böhm Eberhard , Dehnicke Kurt , Strähle Joachim
Published: March 2015

The title compound has been prepared by the reaction of N-trimethylsilyl-iminotriphenylphos-phorane with copper(II) chloride in boiling CCl4 /C2H5OH, and forms moisture sensitive crystals, which are green in transmittance and black in reflexion. [Me3SiNPPh3 · CuCl2 ] 2 was characterized by its IR spectrum as well as by a crystal structure determination (4197 observed, independent reflexions, R = 0.049). The lattice dimensions are at 20 °C: a = 1102.7. b = 1407.3. c = 1560.2 pm; β = 94.27°; space group P21/n with two formula units in the unit cell. The complex consists of centrosymmetric, dimeric molecules with a planar Cu2 Cl2 ring (Cu-CI bond lengths 229 and 231 pm). A terminally bonded CI atom (Cu-CI = 221 pm) and the N atom of the Me3SiNPPh3 ligand (Cu-N = 198.5 pm) complete the coordination number four of the nearly planar surroundings of the Cu atoms.
Darstellung und Kristallstruktur des Bis(triethylammonium)octasulfids, [HN(C2 H5)3]2 S8 / Preparation and Crystal Structure of the Bis(triethylammonium)octasulfide, [HN(C2 H5) 3]2S8
Authors: Schliephake A. , Falius H. , Buchkremer-Hermanns H. , Böttcher P.
Published: March 2015

The preparation and crystal structure of the first octasulfide is described. The reaction of triethylamine, sulfur and dihydrogen sulfide in a solution of formamide yields orange-red crystals of bis(triethylammonium)octasulfide. The crystals are orthorhombic, space group Pbcn. with 4 molecules per unit cell. The cell constants are a = 23.709(4) Å. b = 13.276(4) Å. c = 7.388(2) Å. The chains of sulfur, S8
2-, do not show the common helical all-trans conformation, but a mixed sequence with the signs of the dihedral angles (++−++ and −−+−−).
Lithium-dimethylamino-hydrido-aluminate: Lösungszustand in Diethylether, Tetrahydrofuran und Dimethyldiglykolether / Lithium Dimethylamino Hydrido Aluminates: The Solution State in Diethylether, Tetrahydrofuran and Dimethyldiglycol Ether
Authors: Böck St. , Nöth H.
Published: March 2015

The reaction of LiAlH4 with dimethylamine has been studied in THF, diglyme and diethyl ether solution covering the molar ratios 1:0.5 to 1:4. In all cases the stoichiometric amount of H2 s evolved. With the exception of LiAl[N(CH3)2]4 all other members of the series LiAlH4-n[N(CH3)2]n cannot be isolated. They are in equilibrium with one another in solution, these equilibria are independent of the solvent used.

The structure of compound LiAl[N(CH3)2]4 · 2(OC4H8) has been determined by X-ray diffraction. The anion acts as a bidentate ligand to Li which is also bonded to the oxygen atoms of two THF molecules.
Neue Iminoborane und ihre Reaktionen / Novel Iminoboranes and their Reactions
Authors: Bonn Karl-Heinz van , Bennigsen-Mackiewicz Theo von , Kiesgen Jutta , Plotho Christoph von , Paetzold Peter
Published: March 2015

The iminoboranes RB≡NR′, 2a-f, are formed by the elimination of Me3SiHal from the corresponding aminoboranes 1a-f. Stabilization occurs either through cyclodimerisation (→3b-d,f), cyclotrimerisation (→4e), bicyclotrimerisation (→5b) or cyclotetramerisation (→6a). Trialkylboranes BX3 are added to give the diboryl amines

. 7a-f. The Δ2:-tetraazaborolines

. 8a-f, are the (3+2)-cycloaddition products from 2a-f and azides X′N3. A CH-bond of cyclopentadiene adds to one of the BN bonds of 2f, giving a mixture of the corresponding 1,3- and 1,4-cyclopentadienyl boranes. 9f, 9′f.
Eine Zintl-Phase mit isolierten SnSb4
8-Anionen: Na8SnSb4 / A Zintl Phase with Isolated SnSb4
8- -Anions, Na8SnSb4
Authors: Eisenmann Brigitte , Klein Jürgen
Published: March 2015

The new compound Na8SnSb4 has been prepared from appropriate mixtures of the elements at 700 °C in evacuated silica ampoules coated with glassy carbon. The structure has been determined by single crystal X-ray diffraction data (cubic, space group Fd3m, a - 1481.6(3) pm, Z = 8, R = 0.044 for 263 reflections). There are isolated tetrahedral SnSb4
8- units (bond length Sn -Sb = 284.3 pm), proving the compound to belong to the Zintl phases.
Synthese des 9,9-DimethyI-9-silaacridans sowie einiger Derivate mit variierter Seitenkette / Synthesis of 9,9-Dimethyl-9-silaacridane and of Some Derivatives with Varied N-Side Chains
Authors: Wannagat Ulrich , Wiese Dietma
Published: March 2015

9,9-Dimethyl-9-silaacridane 3a was synthesized by ringclosing reactions of N-trimethylsilyl-bis(2-halogenophenyl)amines with dichlorodimethylsilane and acid cleavage of the silyl groups (eqs (6-9)). Syntheses of N-organyl-substituted 9,9-dimethyl-9-silaacridanes 13 occurred by ring closure of N-organyl-bis(2-halogenophenyl)amines 12 with dichlorodimethylsilane. organyl groups here being dimethylaminoethyl. pyrrolidinoethyl, piperidinoethyl, 3-dimethylamino-2-methyl-propyl and (1-methylpiperidin-3-yl)methyl. 13 were transformed to their hydrochlorides and methoiodides 14. Structures of 13 are compared with those of analogous compounds bearing aminopropyl-side chains and discussed in the light of psychopharmacological effects of tricyclic ring systems.
Struktur und Reaktivität von isoanellierten heterocyclischen Systemen mit 4nπ- und (4n+2)π-Elektronen, XIV [1]: Tri- und tetracyclische Hetarene mit lokalisierten oder delokalisierten PyrroI-Strukturen / Structure and Reactivity of Isoannellated Heterocyclic Systems with 4nπ- and (4n+2)π-Electrons, XIV [1]: Tri- and Tetracyclic Hetarenes with Localized or Delocalized Pyrrole Units
Authors: Kreher Richard P. , Hildebrand Thomas
Published: March 2015

2,7-Di-tert-butyl-2,7-dihydro-benzo[ 1,2-c:3,4-c′]dipyrrole (2b) and 2,5,8-Tri-tert-butyl-5.8-di-hydro-2H-benzo[1,2-c:3,4-c′:5,6-c″]tripyrrole (3b) have been prepared by acetolysis of the cor-responding tri-and tetracyclic N-oxides, isolated in crystallinic form and characterized by spectroscopic data. The scope of the N-oxide route is documented and the existence of benzoannellated pyrroles is proofed. The stabilizing effect of the tert-butyl group is presumably sup-ported by the vicinal annellated heterocycles.
The Crystal Structure of TlBrI2(4-methylpyridine-N-oxide)2
Authors: Hiller W. , Castiñeiras A. , García- Fernandez M. E. , Bermejo M. R. , Bravo J. , Sanchez A.
Published: March 2015

The unit cell of TlBrI2 (4-methylpyridine-N-oxide) 2 is orthorhombic, space group Pnna. with a = 1126.9(3),b = 919.8(2),c = 1210.4(3) pm.and Z = 4. The structure consists of discrete TlBrI2 (4-methyl-pyridine-N-oxide)2 molecules which have a distorted trigonal-bipyramidal geometry. The thallium atom is coordinated to two iodine atoms and a bromine atom in equatorial positions, and by two 4-methyl-pyridine-N-oxide ligands in the axial positions.
Synthesis, Characterization and Complexation Studies with K + and Ca2+ Cations of trans-1.2-Cyclohexanedioxydiacetamides
Authors: Lin Whei Oh , Souza Maria C. B. V. de , Alt Helmut G.
Published: March 2015

The synthesis of trans-1.2-cyclohexanedioxydiacetamides starting with trans-1.2-cyclohexane-diol is described. Eleven of these compounds are characterized by IR, 1H NMR, 13C NMR and mass spectroscopy as well as elemental analyses. Most of these compounds are suitable ionophors for the cations K+ and Ca2+. The coordination sites of these ligands in the 1:2 complexes were determined by IR and NMR spectroscopy
(Ph4P)2 Mn2Br6 und (Ph3PCH2Ph)2Mn2I6 (Ph = C6H5) / (Ph4P)2Mn2Br6 and (Ph 3PCH2Ph)2Mn2I6 (Ph = C6H5
Authors: Pohl Siegfried , Saak Wolfgang , Stolz Peter
Published: March 2015

(Ph4P)2Mn2Br6 (1) and (Ph3PCH2Ph)2Mn2I6 (2) were prepared from the reaction of manganese dihalide with the corresponding phosphonium halide in CH2Cl2.

The structures of 1 and 2 were determined from single crystal X-ray diffraction data.

Both compounds crystallize in the triclinic space group P 1 with one formula unit per unit cell.

1:a = 998.1(1), b = 1005.7(1), c = 1313.3(2) pm, α = 108.51(1), β = 94.25(1), γ = 100.36(1)°.

2: a = 1058.6(2), b = 1236.3(2), c = 1248.4(3) pm, α = 63.53(1), β = 74.15(1), γ = 74.65(1)°.

The structures of 1 and 2 exhibit discrete, dimeric anions formed by the fusion of two identical tetrahedral-like units with a common halogen-halogen edge. The mean Mn-Hal bond lengths were found to be 251.8 pm (Mn-Br) and 272.2 pm (Mn-I). The difference between the bridging and terminal Mn-Hal bond lengths is about 12-13 pm in both compounds
The Molecular Composition of Hydrophilic Sulfur Sols Prepared by Acid Decomposition of Thiosulfate [1]
Authors: Steudel Ralf , Göbel Thomas , Holdt Gabriele
Published: March 2015

Hydrophilic sulfur sols prepared from sodium thiosulfate and concentrated sulfuric acid and purified by repeated NaCl precipitation and peptization in water have been studied by chemical analysis, vibrational spectroscopy, ion-pair chromatography and reversed-phase HPLC. The composition of the sol is Na1.64S28.6O6 · 5.9/n Sn · 1.0 NaCl. The elemental sulfur Sn (n = 6-14; mainly S 8) accounts for 17% the total sulfur; 83% of the S are present as long-chain polythionates which form micelles in which the Sn molecules are dissolved. On aging of the sol at 20 °C the polythionate micelles decompose to give water-soluble short-chain polythionates and elemental sulfur which precipitates from the solution. The micelle structure of hydrophilic sulfur sols may serve as a model for the so-called sulfur globules (S°) formed intra- or extracellularly by many sulfur bacteria which oxidize reduced sulfur compounds to S°. - ᴛ∙nfrared and Raman spectra of K2SmO6 (m = 3-6) are reported. The photodecomposition of aqueous tetrathionate yields sulfite, thiosulfate, and polythionates with up to 9 sulfur atoms
The Crystal Structure of CuSe2Cl
Authors: Milius W. , Rabenau A.
Published: March 2015

The crystal structure of CuSe2Cl has been determined by single-crystal X-ray diffraction. CuSe2Cl crystallizes monoclinically in space group P21/c with the lattice parameters a = 768.3(9) pm, b = 462.5(5) pm and c = 1455.2(3) pm, β = 135.2(4)°, Z = 4. The structure could be shown to be isotypic with CuTe2Cl
Das kantenverknüpfte tritetraedrische Selenostannat(IV)-Anion [Sn3Se8]4-. Darstellung und Struktur von K4Sn3Se8 / The Edge-bridged Tritetrahedral Selenostannate(IV) Anion [Sn3Se8]4-. Preparation and Structure of K4Sn3Se8
Authors: Sheldrick W. S.
Published: March 2015

The potassium selenostannate(IV) K4Sn3Se8 has been prepared by methanolothermal reaction of K2CO3 with elemental Sn and Se at 190 °C and its structure established by X-ray structural analysis. The unit cell contains isolated [Sn3Se8]4- anions consisting of a central SnSe4-tetrahedron edge-bridged to two further tetrahedra. Crystallographic D2-symmetry is observed for these anions. The four-membered rings are markedly distorted with Sn -Se bond distances of 2.520(1) to the central tin atom as compared to long Sn-Se distances of 2.622(1) Å to the tin atoms of the outer tetrahedra. The terminal Sn -Se bonds have a length of 2.473(1) Å.
1,3,5-Tris(dimethylamino)benzol mit Iod und 1,3,5-Tricyanobenzol: Eine ungewöhnliche Dimerisierung und ein „normaler“ Donor/Akzeptor-Komplex / 1,3,5-Tris(dimethylamino)benzene with Iodine and 1,3,5-Tricyanobenzene: An Unusual Dimerization and a “Normal” Donor/Acceptor-Complex
Authors: Keller H. J. , Niebl R. , Renner G. , Ruhr D. von der , Schweitzer D.
Published: March 2015

Reaction of 1,3,5-tris(dimethylamino)benzene (TDMAB) with iodine in solution gives dark red needles of a compound (1) with stoichiometry C24H42I6N6, Mr = 1176.07, orthorhombic, Cmca, Z = 4, a = 10.865(2) Å, b = 16.737(6) Å. c = 20.511(9) Å, V = 3730 Å3, dc = 2.1 g·cm-3 measured at room temperature, R = 0.062 for 744 independent reflections and 100 L. S.-parameters. The solid contains bis[tris(dimethylamino)cyclohexadienylium]dications - obtained by dimerization of TDMAB+ radical cations - and triiodide counter anions. The solid is diamagnetic.

Reaction of TDMAB with 1,3,5-tricyanobenzene (TCB) leads to orange platelets of 2 with stoichiometry C21H24N6, Mr = 360.4, orthorhombic, Pna21 Z = 4, a = 11.074(4) Å, b = 11.568(4) Å, c = 16.100(7) Å, V = 2060 Å3, dc = 1.18 g·cm-3, measured at room temperature, R = 0.065 for 921 independent reflections and 156 parameters. The solid consists of donor (TDMAB) - acceptor (TCB) pairs. The compound is diamagnetic at room temperature.
Synthese und Struktur eines aminstabilisierten Sulfens, RHC=SO2 · N(CH2CH2)3CH / Synthesis and Structure of an Amine Stabilized Sulfene, RHC=SO2 · N(CH2CH2)3CH
Authors: Hartwig Uwe , Pritzkow Hans , Sundermeyer Wolfgang , Waldi Joachim
Published: March 2015

The structure of the quinuclidine-stabilized mesyl sulfene H3C-SO2-CH=SO2←N(CH2CH2)3CH (3) was determined by X-ray analysis, which indicates a double-bond in the C=SO2 group, while the quinuclidine is coordinated at a distance to the sulfur atom longer than a S-N single bond.
Darstellung, Reaktionen und Kristallstrukturen von (Me3NCH2Ph)2 Fe2I6 und Fe2I4(SPPh3)2 · PhMe (Ph = C6H5, Me = CH3) / Preparation, Reactions, and Crystal Structure of (Me3NCH2Ph)2Fe2I6 and Fe2I4(SPPh3)2 · PhMe (Ph = C6H5, Me = CH3)
Authors: Saak Wolfgang , Haase Detlev , Pohl Siegfried
Published: March 2015

The reaction of FeI2, with (Me3NCH2Ph)I in CH2Cl2 and with Ph3PS in toluene (molar ratios 1:1) yields (Me3NCH2Ph)2Fe2I6 (1) and Fe2I6(SPPh3)2·C6H5CH3 (2), respectively. The structures of 1 and 2 were determined from single crystal X-ray diffraction data. 1 crystallizes in the monoclinic space group P21/n with a = 895.7(2), b = 1400.5(2), c = 1360.6(3) pm. β = 95.82(2)°, Z = 2. The anion of 1, Fe2I6
2-, has edge-sharing double-tetrahedra. The bridging and terminal F e - I bond lengths were found to be 269.9/270.7 and 260.3/258.6 pm, respectively (Fe-Fe: 358.2 pm). 2 crystallizes in the triclinic space group P1̄ with a = 987.6(1), b = 1119.3(1), c = 1159.4(1) pm, α = 101.10(1), β = 99.15(1), γ = 102.83(1)°, Z = 1. The molecules of 2 consist of centrosymmetric dinuclear Fe2I2 units (like for Fe2I6
2- in 1), with F e - I distances of 266.4 and 273.4 pm. The distorted tetrahedra around Fe are completed by an iodide ion (Fe-I: 256.9 pm) and Ph3PS with the sulfur as donor atom. The Fe-Fe distance was found to be 339.7 pm.
Studies on Organomercury(II) Complexes of Isoniacinamide
Authors: Bhatia Sangeeta , Kaushik N. K. , Sodhi G. S.
Published: March 2015

Organomercury(II) complexes involving isoniacinamide(I) of the type. RHgCl(L)(II) [R = phenyl, o-, p-hydroxyphenyl ( o-, p-HOC6H4) , p-acetoxyphenyl (p-AcOC6H4), 2-furyl (2-C4H3O); L = isoniacinamide] have been synthesized and characterized. Conductance measurements indicate that the complexes are non-electrolytes. From IR and UV spectral studies it is concluded that isoniacinamide is coordinated to the mercury(II) ion through the ring nitrogen atom. 1H and 13C NMR support the stoichiometry of the complexes. Fluorescence studies have been made for o-, p-HOC6H4HgCl(L) complexes. For C6H5HgCl(L), p-HOC6H4HgCl(L) and p-AcOC6H4HgCl(L) complexes, thermal studies (TG and DSC) have been carried out and relevant kinetic and thermodynamic parameters for thermal degradation have been enumerated. The fragmentation pattern of the complexes has been analysed on the basis of mass spectra. The C6H5HgCl(L) and p-AcOC6H4HgCl(L) complexes have been screened for antibacterial activity.
Notizen: Neuartige basische Liganden für die homogenkatalytische Methanolcarbonylierung, XV [1]. (Ether-Phosphan)-stabilisierter cis-Dihydrido-Rhodium(III)-Komplex / Novel Basic Ligands for the Homogenous Catalytic Methanolcarbonylation, XV [1]. (Ether-Phosphane)-Stabilized cis-Dihydrido-rhodium(III) Complex
Authors: Lindner Ekkehard , Andres Berthold
Published: March 2015

Reaction of [Rh(NBD)(P∼O)2][SbF6] (1) (NBD = norbornadiene) with hydrogen results in the formation of the stable dihydrido rhodium complex [cis-

(2). Rh - O bond cleavage in 2 by carbon monoxide or NaBH4 affords the products [trans-(P∼O)2Rh(CO)3][SbF6] (3) and [trans-H2Rh((P∼O)2(η2-H2BH2)] (5), respectively. Upon treating a THF solution of 3 with argon, 3 eliminates CO to give the complex

(4) with a mono- and bidentate (ether-phosphane) ligand.
Darstellung und Redoxverhalten aller bindungsisomeren Hexakis(thiocyanato(N)-thiocyanato(S))-osmate(III) und (IV), [Os(NCS)n(SCN)6-n]3-/2-, n = 0—6, einschließlich der Stereoisomeren / Preparation and Electrochemical Behaviour of All Bond-Isomeric Hexakis(thiocyanato(N)-thiocyanato(S))osmates(III) and (IV), [Os(NCS)n(SCN)6-n]3-/2-, n = 0—6, Including Stereoisomers
Authors: Bütje K. , Preetz W.
Published: March 2015

The first two complete series of all 10 possible linkage and geometric isomers of the general formula [Os(NCS)n(SCN)6-n]3-/2- have been obtained. The Os(III) complexes, some of which have been previously known, are prepared from the reactions of K2[OsX6], X = Cl. Br. I, and K2[OsO2(OH)4] with excess aqueous or methanolic KSCN solution and subsequent chromato­graphic separation on DEAE cellulose. Oxidation with Ce(IV) in acetone or methanol yields the corresponding Os(IV) compounds without changes in the ligand sphere except for n = 0, but pure salts of [Os(SCN)6]2“ are isolated by repeated recrystallization. S-bonding is less favoured in Os(IV) than in Os(III), proving that Os(IV) is the harder Lewis acid. Cyclic voltammograms of all isomers show two waves, a mainly irreversible Os(II)/Os(III) couple and a reversible Os(III)/Os(IV) couple. Characteristic shifts of the half-wave potentials of both electron transfer reactions within the series give strong evidence of π-back donation to -NCS.
Pentamethylcyclopentadienyl-, Acetylcyclopentadienyl- und Indenyl-dicarbonyl-AcetylenkompIexe des Vanadiums. Molekülstruktur von C9H7V(CO)2PhC2H / Pentamethylcyclopentadienyl, Acetylcyclopentadienyl and Indenyl Dicarbonyl Acetylene Complexes of Vanadium. Molecular Structure of C9H7V(CO)2PhC2H
Authors: Alt Helmut G. , Engelhardt Heidi E. , Razavi Abbas , Rausch Marvin D. , Rogers Robin D.
Published: March 2015

The photo-induced reaction of C5Me5V(CO)4 (1). (C5H4COMe)V(CO)4 (2) and C9H7V(CO)4 (3) with acetylenes R1C2R2 (R1, R2 = H. Me, Ph) yields the substitution products C5Me5V(CO)2R1C2R2 (4), (C5H4COMe)V(CO)2R1C2R2 (6) and C9H7V(CO)2R1C2R2 (7). One CO ligand of complexes 4 can be substituted by PMe3 affording complexes of the type C5Me5V(CO)(PMe3)R1C2R2 (5). The acetylene complexes 4-7 are characterized by their IR. 1H, 13C and 51V NMR as well as their mass spectra. In these compounds the alkyne ligand shows a hindered rotation around the metal alkyne bond axis. The rotation barrier (ΔG≠ = 40-50 kJ/mol) is higher than in the corresponding cyclopentadienyl complexes. An X-ray crystal structure analysis of C9H7V(CO)2PhC2H indicates an orientation of the alkyne-C-C-axis in the symmetry plane of the C9H7V(CO)2 fragment. The phenyl substituent is pointing away from the metal and the indenyl ligand.
Beiträge zur Chemie des Bors, 190 [1] Synthese und Molekülstruktur von 1,2-Dihydroboreten und Azadiboretidinen / Contribution to the Chemistry of Boron, 190 [1] Synthesis and Molecular Structure of 1,2-Dihydrodiboretes and Azadiboretidines
Authors: Glaser Bernhard , Mayer Erwin P. , Nöth Heinrich , Rattay Wilfried , Wietelmann Ulrich
Published: March 2015

[2+2]-Cycloadditions of 9-Fluorenylidentetramethylpiperidinoboranes have been studied with selected olefines, acetylenes and iminoboranes. No reactions with olefines were observed. While propiolic methylester reacts exclusively at the carbonyl bond producing the oxaboretane 5, alkines such as diethylamino-alkines, cyclo-octine and phenylacetylene provide access to the'1,2-dihydroboretenes 6, 3 and 2. Tetramethylpiperidinoiminoboranes make 1.2.4-azadiboretidines 7 available.

6a and 7a contain a folded four-membered ring as shown by X-ray structure analysis. There is only a weak 1,3-intraannular interaction due to BN-;r-bonding of the boron atoms with their exocyclic amino group.
On the Synthesis and Electrochemical Properties of Some New Bipyridinium and Related Compounds
Authors: Bauer Rupert , Nussbaumer Peter , Neumann-Spallart Michael
Published: March 2015

The synthesis of some new bipyridinium salts is described. Their behavior upon reduction is studied by cyclovoltammetry, coulometry and spectroscopically. Halfwave potentials range from -0.28 V to -0.59 V and ε values of the reduced viologens lie around 104 M-1cm -1 . In addition two relay compounds (4,4′-pyridine-2,4-diyl)-bis-(1-methylpyridinium methylsulfate), 4.4′,4″-(pyridine-2,4,6-triyl)-tris-(1-methylpyridiniumchloride) that are not viologens are described. These substances also form a colored radical upon reduction, but with exceptional stability to-wards oxidation with dioxygen. From coulometric measurements it is inferred that three electrons are transferred in one step. Spectral changes observed in the course of the electrochemical reduction are explained by dimer formation.
Molekülstruktur von {[P(C6H5)3]2RhOH}2· 2 C6H6 / The Molecular Structure of {[P(C6H5)3]2RhOH}2· 2 C6H6
Authors: Brune Hans-Albert , Hemmer Reinhard , Unsin Josef , Holl Konrad , Thewalt Ulf
Published: March 2015

The dinuclear Rhodium(I) complex Bis(μ-hydroxo)bis(bistriphenylphosphane-rhodium) forms during the HRh(PPh3)2 catalyzed hydrogenation of Schiff bases by isopropanol. It can be isolated from benzene solution as a crystalline solvate of composition {[P(C6H5)3]2RhOH}2·2 C6H6 (1). The complex contains a four-membered ring with bridging hydroxo groups. Crystals of 1 are triclinic, space group P1̄ with a = 12.570(3), b = 12.850(4), c = 13.982(3) Å, α = 116.23(3), β = 115.08(3), γ = 90.89(3)°, and Z = 1.
Stickstoffverbindungen von Elementen der dritten Hauptgruppe mit intra- und intermolekularen Donor-Akzeptor-Bindungen, V [1]. Spezielle Gallium- und Indiumamide mit Alkoxogruppen / Nitrogen Compounds of Elements of the Third Main Group with Intra- and Intermolecular Donor Acceptor Bonds, V [1]. Special Gallium and Indium Amides with Alkoxo Groups
Authors: Veith M. , Pöhlmann J.
Published: March 2015

The lithium alkoxoamidosilane (Me2Si(OtBu)(NtBu)Li)2 (4) and its trimethyltin derivative Me2Si(OtBu)(NtBu)SnMe3 (7) have been used, to introduce the ligand Me2Si(OtBu)(NtBu) = L into molecular compounds of gallium and indium. The following molecules were synthesized: L-M(Me)Cl (M = Ga (5), In (6)), L-InMe2 (8), L-InX2 (X = Cl (9), Br (10)), L2InX (X = Cl (11), Br (12)) and L2Ga2Cl2 (22). The ligand L is assumed to chelate the metal atom on the basis of temperature dependent 1H NMR spectra. The chelating effect is more pronounced in the gallium derivatives than in the indium analogues. Equilibria between L2InX/InX3 and LInX2 have been observed in diethylether solutions. No metal(I) derivatives LGa or LIn could be isolated. L2Ga2Cl2 (22), formally containing gallium(ll), can be sublimed without decomposition at 110 °C in vacuo.
Synthese und Struktur des ersten dreigliedrigen Arsen—Phosphor—Platin-Ringes / Synthesis and Structure of the First Three-Membered Ring Containing Arsenic, Phosphorus and Platinum
Authors: Edelmann Frank , Spang Claudia , Roesky Herbert W. , Jones Peter G.
Published: March 2015

2,4,6-Tri-butylphenylphosphane reacts with CpFe(C5H4AsCl2) in the presence of DBU to yield CpFe[C5H4As=PC6H2(t-Bu)3]. The reaction of this arsaphosphene with (Ph3P)2PtC2H4 yields

, a three-membered ring containing arsenic, phosphorus and platinum.
Synthese und Struktur von 1,5-Bis(tolyl)pentaazadienidokomplexen von Eisen(II) und Ruthenium(I): [Fe(tolN5tol)2]2 und [Ru(CO)3(tolN5tol)]2 / Synthesis and Structure of 1,5-Bis(tolyl)pentaazadienido Complexes of Iron(II) and Ruthenium(I): [Fe(tolN5tol)2]2 and [Ru(CO)3(tolN5tol)]2
Authors: Schmid Raimund , Strähle Joachim
Published: March 2015

The reaction of Fe(CO)4I2 with Ag(tolN5tol) in THF yields dark violet, oxygen sensitive [Fe(tolN5tol)2]2 (1), whereas in the case of Ru(CO)4I2 the reaction with Ag(tolN5tol) occurs under reduction to Ru(I), and brownish, air stable [Ru(CO)3(tolN5tol)]2 (2) is obtained.

1 crystallizes from THF as 1·THF in the monoclinic space group P21/c with a = 1395.7(4), b = 2226.5(9), c = 1973.5(7) pm. β = 105.10(2)°, Z = 4. In the binuclear complex four pentaazadienido anions act as (N1,N3)-η2, (N5)-η1 bridging ligands coordinating the Fe atoms octahedrally. 2 forms triclinic crystals with the space group P1̄ and a = 1368.6(6), b = 1393.7(6), c = 1076.1(5) pm, α = 104.59(4)°, β = 107.36(4)°, γ = 73.90(3)°, Z = 2. Two pentaazadienido ligands bridge two Ru(CO)3
+ units with their atoms N1 and N3. In addition, the Ru atoms are connected by a Ru-Ru single bond of 267.5 pm. In 1 as well as in 2 the pentaazadienido ligands exhibit planar N5 zigzag chains in the all-trans configuration. The N -N-distances are in the range of 124.2 to 137.4 pm.
Zur Chemie und Strukturchemie von Phosphiden und Polyphosphiden, 49 [1]. Bildung und Struktur des Henicosaphosphids [Li(12-Krone-4)2]3P21(THF)2 / Chemistry and Structural Chemistry of Phosphides and Polyphosphides, 49 [1]. Formation and Structure of the Henicosaphosphide [Li(12-Crown-4)2]3P21(THF)2
Authors: Fritz Gerhard , Schneider Hans-Werner , Hönle Wolfgang , Schnering Hans Georg von
Published: March 2015

The reaction of Li3P7(DME)3 with crown ether 12-crown-4 and (CHT)Cr(CO)3 yields a reddish oil, from which red crystals of [Li(12-crown-4)2]3P21(THF)2 (1), red crystals of Li2P16(12-crown-4)x(THF)2 as well as a not yet identified yellow substance separates. From this mixture crystals of 1 could be isolated. [Li(12-crown-4)2]3P21(THF)2 (1) crystallizes in the space group P21/a with a = 3021.1(6) pm, b = 1901.5(4) pm, c = 1603.0(4) pm, β = 95.98(3)° and Z = 4 formula units in the unit cell. The structure is characterized by isolated 1
∞[P21
3-] trianions and Li(12-crown-4)2 cations. The trianion has approximately the symmetry mm2. The bond distances d(P-P) range from 213.9 pm to 226.8 pm and are differentiated by their function in the skeleton. The bond angles β(P-P-P) are in the range 86.1° to 107.7° and image clearly the influence of the repulsion of the non-bonded electron pairs of the strained anion. The curvature of the trianion is approx. 0.8 nm-1 and is three times larger than the curvature evaluated from structural models.
1,1-Disilylethan, CH3CH(SiH3)2 / 1,1-Disilylethane, CH3CH(SiH3)2
Authors: Schmidbaur Hubert , Hager Rudolf
Published: March 2015

1,1-Bis(trichlorosilyl)ethane, CH3CH(SiCl3)2 (1) is readily available through catalytic hydrosilylation of vinyltrichlorosilane and silicochloroform (90% yield), or through the base-induced reduction of acetyl chloride using again silicochloroform (60%). 1 can be converted into the title compound 2 in 80% yield by lithium aluminium hydride in di-n-butylether. Compound 2 is a highly volatile liquid (bp. 40-42 °C), not spontaneously inflamable in air. which is of interest as a precursor for chemical vapour deposition of hydrogen-containing silicon/carbon alloys (a-Si, C:H) and silicon carbide. Based on thermodynamical data, it is the least stable isomer of the composition C2Si2H10.
Bindungsisomere Hexakis(selenocyanato(N)-selenocyanato(Se))-Osmate(III), [Os(NCSe)n(SeCN)6-n]3-, n = 0-3 / Bond Isomeric Hexakis(selenocyanato(N)-selenocyanato(Se)) Osmates(III), [Os(NCSe)n(SeCN)6-n]3-, n = 0-3
Authors: Bütje K. , Preetz W.
Published: March 2015

Six of ten possible linkage and geometric isomers of the formula [Os(NCSe)n(SeCN)6-n]3-, n = 0-3, have been obtained. The n = 0-2 complexes are prepared from the reactions of K2[OsX6] , X = Br, I, and of K2[OsO2(OH)4] in presence of ascorbic acid, with excess aqueous or methanolic KSeCN solutions at 20-40 °C. By heating the solid tetrabutylammonium salts, N-bonding of the ambident SeCN- is favoured, and the n = 3 species are formed. The complexes are separated by ion exchange chromatography and characterized by vibrational and electronic spectra. Characteristic group frequencies are: νOsSe: 183 - 216, νOsN: 224-246, νCSe(Se): 508-528, νCSe(N): 665-680, νCN: 2081-2122 cm-1.
NMR-spektroskopische Untersuchung des Problems der Valenzisomerie zwischen 1,2-Dithiin und (Z)-But-2-en-1,4-dithion / NMR Spectroscopic Investigation Concerning the Problem of Valence Isomerism between 1,2-Dithiine and (Z)-But-2-ene-1,4-dithione
Authors: Radeglia Reiner , Poleschner Helmut , Schroth Werner
Published: March 2015

3,6-Diaryl-1,2-dithiines and their precursors, (Z,Z)-1,4-bis(organylthio)-buta-1,3-dienes, are investigated by 1H and 13C NMR spectroscopy. The chemical shifts and coupling constants, which are relevant to the investigated problem, are determined and assigned, respectively, by different techniques (shift increments, spectrum simulation, heteronuclear 2D J-resolved and heteronuclear shift correlated 2D NMR spectra, anomalous off-resonance splittings and selective decoupling experiments). The NMR parameters are discussed in relation to the molecular structure. The 13C shift values prove the ring structure of 1,2-dithiines and exclude existence of the valence isomer (Z)-but-2-ene-1,4-dithione (absence of thiocarbonyl resonances). The vicinal 1H,1H coupling constants of the C4 unit of the investigated compounds verify (1) the (Z,Z) configuration of the organylthio groups in 1,4 position of butadiene, (2) the s-transoid conformation of acyclic butadienes and (3) the forced s-cis structure in the cyclic 1,2-dithiines.
Notizen: Zur Reaktion von [(η3-C4H7)PdCl]2 mit Se(SiMe3)2 Die Kristallstruktur von [(η3-C4H7)6Pd6Se3] / Reaction of [(η3-C4H7)PdCl]2 with Se(SiMe3)2 The Crystal Structure of [(η3-C4H7)6Pd6Se3]
Authors: Fenske Dieter , Hollnagel Achim , Merzweiler Kurt
Published: March 2015

[(η3-C4H7)PdCl]2 reacts with Se(SiMe3)2 to form [(η3-C4H7)6Pd6Se3] (1). 1 has been characterized by X-ray crystal structure analysis. It contains a distorted trigonal prismatic Pd6-cluster. Three faces of the Pd-prism are occupied by μ4-Se ligands. 1 crystallizes in the space group Pnma with 4 formula units per unit cell. The lattice constants at 200 K are: a = 1175.1(8), b = 1611.4(12), c = 1720.3(12) pm.
Notizen: Das Infrarotspektrum des Tetraselentetranitrids, Se4N4 / The Infrared Spectrum of Tetraseleniumtetranitride, Se4N4
Authors: Adel Jörg , Ergezinger Christina , Figge Reiner , Dehnicke Kurt
Published: March 2015

The IR spectrum of solid Se4N4 has been recorded in the region of 100- 4000 cm-1 . The assignment has been made on the basis of slightly deformed D2d symmetry, which is in agreement with the X-ray structure determination.
Neue Synthesewege zu B4H10 und B5H9 / New Synthetic Routes to B4H10 and B5H9
Authors: Breilochs Bernd , Binder Herbert
Published: March 2015

The boron hydride B4H10 is prepared in high yields (90%) through hydride-ion abstraction reactions when a mixture of BH4
-/B4H8
- is treated with CH3I or I2 respectively. A high yield (96%) method for the conversion of B3H8 to B4H10 is the reaction of B3H8
- with AICl3 solvents which do not have any Lewis base character. The solvents are assumed to react as electron acceptors with the intermediate [B2H5
-] to form B4H10, R- and H2 (R-H = solvent). A 1:1 mixture of B4H10, and B5H9 is obtained when B3H8
- is treated with CH3I or I2. The reaction can be viewed to involve an initial step in which unstable “B3H7” is generated which immediately undergoes decomposition to give B4H10, B5H9 and H2. Treatment of B4H10 with (n-Bu)4NBr results in the formation of B4H7Br- which decomposes slowly at 0 °C to form B5H9. An alternative synthesis of B5H9, via hydride-ion abstraction is possible through the reaction of (n-Bu)2O-BF4 with B3H8
- in ether solvents.
N-Chlornitrenokomplexe des Wolframs: WCl4 (NCl) und [CH3CN-WCl4 (NCl)] / N-Chloro-Nitrene Complexes of Tungsten:WCl4 (NCl) and [CH3CN-WCl4 (NCl)]
Authors: Görge Astrid , Dehnicke Kurt , Fenske Dieter
Published: March 2015

WCl4(NCl) has been prepared as a red-brown crystal powder by the reaction of tungsten hexacarbonyl with excess nitrogen trichloride in boiling CCl4. The complex is associated via chloro bridges, forming dimeric units, according to the IR spectrum. Thermal decomposition at 200 °C leads to tungsten nitride trichloride, WNCl3,. With acetonitrile, WCl4(NCl) reacts with formation of the monomeric complex [CH,CN-WCl4(NCl)], which was characterized by its IR spectrum as well as by an X-ray structure determination. Crystal data: space group P21/m, Z = 2 (1387 independent observed reflexions, R = 0.07). Lattice dimensions at 20 °C: a = 590.4(3), b = 729.0(3), c = 1124.6(4) pm, β = 100.63(2)°. The complex forms monomeric molecules, in which the tungsten atom has a distorted octahedral environment of four chlorine atoms in equatorial positions, and the acetonitrile molecule in trans-position to the

group. Bond lengths WN = 172 and NCI = 161 pm; bond angle WNCl = 175.5°.
Dreikernkomplexe mit Ferrocen-1,1'-dithiolat-Brücke / Trinuclear Complexes Containing a Ferrocene-1,1'-dithiolato Bridge
Authors: Herberhold Max , Ott Jutta
Published: March 2015

Trimetallic complexes Fe(C5H4-SMLn)2 (MLn = M(NO)2Cp (M = Cr. Mo, W) and M(CO)3 Cp (M = Mo, W)) containing a ferrocene-1.1'-dithiolato bridge between two group VI metals were prepared and spectroscopically characterized. The mixed species Fe(C5H4-SCr(NO)2Cp)(C5H4-SW(CO)3Cp) and the bimetallic precursors Fe(C5H4-SMLn)(C5H4-SH), (MLn=M(NO)2Cp(M=Cr,Mo), M(CO),Cp(M=Mo,W)). were also obtained. The ferrocene-thiolato ligands are stronger electron-donors than phenyl-and methyl-thiolato ligands.
Synthese und Multikern-NMR-Spektroskopie einiger vier-und fünfgliedriger Zinn—Stickstoff-Heterocyclen / Synthesis and Multinuclear NMR Spectroscopy of Some Four-and Five-Membered Tin —Nitrogen Heterocycles
Authors: Stader Carin , Wrackmeyer Bernd , Schlosser Dieter
Published: March 2015

Tin-nitrogen heterocycles [1,3,2,4λ2-diazasila- (1), -λ4-stannetidines (2), spiro-compounds (3, 4), 1,3,2λ4,4λ4-diazadistannetidines (5), 1,3,4,5,2λ2-diazadisila- (6) and -λ4-stannolidines (7)] have been characterized by 13C, 15N, 29Si and 119Sn NMR spectroscopy [chemical shifts δX and coupling constants nJ(119Sn-X) (n = 1, 2, 3; X = 13C, 15N, 29Si, 119Sn]. The influence of the ring size becomes apparent in particular by comparison of the various coupling constants. In the compounds 1 and 6 the presence of a two-coordinate tin atom is reflected by the extremely low shielding of the 119Sn nuclei and also by the reduced shielding of the 29Si nucleus. The comparison with δ(29Si) data for corresponding non-cyclic compounds indicates that the latter effect may be traced to intra-annular interactions in 1 and 6 which involve the lone electron pair at the tin atom.
Übergangsmetall-substituierte Diphosphene, XIV. Zur Reaktivität des Diphosphenylkomplexes (μ5-C5Me5)(CO)2Fe—P=P—Ar (Ar = 2,4,6-t-Bu3C6H2) gegenüber Schwefel, Selen und Tellur. Synthese und Struktur des ersten Thioxo-λ5-diphosphenyl-Komplexes (μ5-C5Me5)(CO)2Fe-P(=S)(=P-Ar) / Transition Metal Substituted Diphosphenes. On the Reactivity of the Diphosphenyl Complex (μ5-C5Me5)(CO)2Fe-P=P-Ar (Ar = 2,4,6-t-Bu3C6H2) towards Sulfur, Selenium, and Tellurium. Synthesis and X-Ray Structure Analysis of the First Thioxo-λ5-diphosphenyl Complex (μ5-C5Me5) (CO)2Fe - P(=S)(=P - Ar)
Authors: Weber Lothar , Meine Georg , Boese Roland , Niederprüm Norbert
Published: March 2015

The diphosphenyl complex (μ5-C5Me5)(CO)2Fe-P=P-Ar (1a) (Ar = 2,4,6-tert-Bu3C6H2) reacts with an equimolar amount of sulfur to yield the first thioxo- λ5 -diphosphenyl complex (μ5-C5Me5)(CO)2Fe-P(=S)=P-Ar (2). Heating of 2 in boiling benzene affords the metal functionalized thiadiphosphirane 3. Similarily the selenoxo-λ5 -diphosphenyl complex (μ5-C5Me5)(CO)2Fe-P(=Se)=P-Ar (5) and selena-diphosphirane 6 are synthesized. The products have been characterized by elemental analysis as well as by spectroscopic data (IR, 1H, 13C, 31P NMR, MS). The molecular structure of 2 has been elucidated by single crystal X-ray analysis.
Synthese der ersten quadratisch-planaren Vinyliden-Komplexe des Vaska-Typs. Kristall- und Molekülstruktur von trans-[RhCl(=C=CHMe)(PPri
3)2] / Synthesis of the First Square-planar Vinylidene Complexes of the Vaska Type. Crystal and Molecular Structure of trans-[RhCl(=C=CHMe)(PPri
3)2]
Authors: Werner Helmut , Alonso Francisco Javier Garcia , Otto Heiko , Wolf Justin
Published: March 2015

Square-planar vinylidene rhodium complexes trans-[RhCl( = C=CHR)(PPri
3)2] (X-XII) are prepared either by isomerization of trans-[RhCl(RC≡CH)(PPri
3)2] in hexane at 50 °C or by elimination of pyridine from RhHCl(C≡CR)(py)(PPri
3)2 in benzene at room temperature. The Xray structural analysis of XI (R = CH3) reveals that the CI-Rh=C=C fragment is almost linear, and that the planes formed by these atoms and C3 (carbon atom of the CH3 substituent) and by these atoms and P1 , P2 are perpendicular to each other. The Rh = C bond length is surprisingly short (177.5(6) pm) and supports the assumption that vinylidenes like CO are strong π-acceptor ligands.