bluuebunny/crossref_metadata_2025 huggingface dataset:
Ru2(CO)6(ButNS) − Ein tert-Butylschwefelimid-Komplex mit Ru2NS-Tetrahedrangerüst / Ru2(CO)6(BUtNS) - A tert-Butyl Sulfur Imide Complex Containing a Ru2NS Tetrahedrane Skeleton
Authors: Herberhold Max , Bühlmeyer Wolfgang , Gieren Alfred , Hübner Thomas , Wu J.
Published: March 2015

Fragmentation of bis(rm-butyl) sulfur diimide, S(NBut)2 (1a), in the presence of Ru3(CO)12 leads to a yellow tetrahedrane-type complex Ru2(CO)6(ButNS) (3a) containing tert-butyl sulfur imide as a six-electron ligand. According to the X-ray structure determination the N−S bond (1.716 Å) is arranged perpendicular to the Ru−Ru axis (2.661 Å).
A Study on the Mannich Reaction with 1-Phenylamino-3-indenone
Authors: Hammouda M. , Hamama W. S. , Afsah E. M.
Published: March 2015

Mannich reaction of the title compound 1 with formaldehyde and morpholine, piperidine or piperazine afforded the Mannich bases 3-5 respectively, whereas the indeno[1.2-d]pyrimidines (6-7) were obtained where primary amines were used. Treatment of 2 with formaldehyde gave benz[b]indeno-diazepine (8). The reaction of formaldehyde with 1 was also investigated.
Cyclische Organylarsino-Schwefeldiimide / Cyclic Organylarsino Sulfur Diimides
Authors: Herberhold Max , Guldner Karlheinz
Published: March 2015

The reactions of the bifunctional bis(chloroarsino) compounds MeCH[As(But )Cl]2 and RCH[AsCl2]2 (R = H, Me) with the salt K2SN2 lead to rings and cages containing arsino-substituted sulfur diimide units.
Oxo-und Thiovanadium(V)-Thiolate/Oxo and Thiovanadium(V) Thiolates
Authors: Preuss Fritz , Noichl Harald
Published: March 2015

Syntheses of oxovanadium(V) thiolates such as O = V(SR)3 (R = tC4H9 , SiPh3 ) and O=V(OtC4H9 )n(StC4H9)3-n(n = 1, 2) are described. The thiovanadium(V) compounds S=V(OtC4H9 )3 , S = V(StC4H9)(OtC4H9) 2 and S=V(SSiPh3)3 have been prepared by various methods :substition

using Lawesson reagent, oxidation of V(OtC4H9)4 by sulfur, or disproportionation reaction of VCl4 with LiSSiPh3 ; O = V (OSiR3)3 (R = Me , Ph) undergoes a reaction with Lawesson reagent to yield dithiophosphonate complexes. All compounds obtained are characterized by 1H and 51V NMR spectroscopy; the stability of thiovanadium(V) compounds is discussed. V(StC4H9)4 has been synthesized as a first example of vanadium(IV) thiolates
Zur Kenntnis von KCrF4/On KCrF4
Authors: Kissel Dieter , Hoppe Rudolf
Published: March 2015

KCrF4 has been prepared as yellowish-green single crystals (by heating of KF, CuF2 , CrF3 ; Au-tube, 750 °C, 60d). It crystallizes in the orthorhombic crystal system (Pnma) with: a = 1573.2, b = 743.2, c = 1833.1 pm, Z = 24. The structure shows [Cr3F9F6/2]3--columns along [010], The Madelung Part of Lattice Energie, MAPLE, is calculated and discussed, along with Effective Coordination Numbers, ECoN (via Mean Fictive Ionic Radii, MEFIR). The structure is described using SCHLEGEL-diagrams.
Cyclophan-Metall-Komplexe: Synthese und Kristallstruktur von ([2](l,4)Naphthalino[2]paracyclophan)gallium(I)-tetrabromogallat(III)/Cyclophane Metal Complexes: Synthesis and Crystal Structure of ([2]( 1,4)Naphthalino[2]paracyclophane)gallium(I) Tetrabromogallate(III)
Authors: Schmidbaur H. , Bublak W. , Müller G.
Published: March 2015

The title complex has been prepared from Ga[GaBr4] and [2](1,4)naphthalino[2]paracyclophane in toluene as a solvent, and the crystal structure of this adduct determined by single crystal X-ray diffraction. The structure is composed of dimeric units Ga2[GaBr4]2 , which are crosslinked into sheets through Ga(I)-arene coordination. Both the benzene ring and the substituted ring of the naphthalene system are η6-bonded from the outer side of the cyclophane cage, each to an univalent metal. The benzene and the naphthalene form an interplane angle of 49.3°. The distance to the benzene ring (2.67 Å) is much shorter than the distance to the naphthalene (2.85 Å), suggesting a stronger complexation with the unperturbed π-system of the former. [2.2](l,4)Naphthalinophane forms no adduct with Ga[GaBr4], and with [2](l,5)naphthalino[2]paracyclophane secondary reactions are observed.
Reaktionen von 2,3-Dihydro-1,3-diborolen mit Kalium und Iodmethan. Charakterisierung der Produkte als (C5H5)Co-Komplexe/ Reactions of 2,3-Dihydro-1,3-diboroles with Potassium and Iodomethane. Characterization of the Products as (C5H5)Co Complexes
Authors: Stumpf Klaus , Siebert Walter , Köster Roland , Seidel Günter
Published: March 2015

The reactions between 2,3-dihydro-1,3-diborole derivatives 1 and potassium in tetrahydrofuran yield dark brown solutions. Without elimination of hydrogen, 1.4 to 1.8 moles of potassium are consumed by one mole of 1. Reduced 1 and iodomethane react to give methylated products, identified by GC/MS studies. Complexation with (C5H5)Co(C2H4)2 leads to the cyclopentadienyl-cobalt complexes 2, iso-2, 3, and 4, of which iso-2 is a new cobalt-hydride sandwich. Methylation reactions of the cobalt sandwich anions (2-H)- are reported.
Interaction of Metal Ions with 7-Deaza-8-aza-and 8-Aza-purines Preparation and X-Ray Structural Analysis of Copper(II) Complexes
Authors: Sheldrick W. S. , Bell P.
Published: March 2015

The reaction of 8-aza-and 7-deaza-8-aza-purines with Cu2+ cations in acid solution has been studied. At a pH value of 2, the 8-azaadenine complex [Cu(H2O)4(AAdH)2](NO3)2 (1), which displays Cu-N9 coordination, may be isolated from solution. The reaction of CuCl2 with 8-aza-hypoxanthine in concentrated HCl solution leads to ring opening at C2 of the azapurine with subsequent formation of dichlorobis[(5-amino-4-carboxamide)[1 - 3]triazole] copper(II) dihydrate 2, in which the triazole ligands display a chelating function, coordinating the metal via N7 and O6. The results for 1 and 2 suggest that copper coordination of the azapurine base is not a prerequisite for opening of the pyrimidine ring. Respectively N9-and N8-coordinated complexes [CUCl3(AllH3)]n 3 and [CuCl2(H2O)(MAllH)]n (4) of allopurinol (AllH2) and 9-methylallopurinol (MAllH) may be prepared by the reaction of CuCl2 with the respective bases in HCl solution. In contrast, with the analogous 1-methyl-4-aminopyrazolo[3,4-d]pyrimidine MAPP, only the salt (MAPPH)4(CU2Cl8) (5) could be isolated under similar conditions, indicating that N8 is less attractive as a binding site in this 7-deaza-8-azaadenine derivative. The structures of 1-5 have been established by X-ray structural analysis. A distorted octahedral [4+2]geometry is found for the copper atoms in 1 and 2. Chlorine bridged polymeric chain structures are adopted by the complexes 3 and 4. An intermediate coordination geometry between trigonal bipyramidal and square-pyramidal is observed for the metal atoms in 3, a distorted square-pyramidal geometry in 4.
Diazoverbindungen, 65 Isomerisierungen im System 4-Diazo-1-buten/2.3-Diazabicyclo[3.1.0]hex-2-en/1.4-Dihydropyridazin/Diazo Compounds, 65 Isomerization Reactions in the System 4-Diazo-1-butene/2.3-Diazabicyclo[3.1.0]hex-2-ene/1.4-Dihydropyridazine
Authors: Heydt Heinrich , Breiner Hans-Werner , Hell Volker , Regitz Manfred
Published: March 2015

(Diazomethyl)diphenylphosphine oxide (2a) adds onto the 1-cyclopropene phosphonates 1a and c under formation of the 2.3-diazabicyclo[3.1.0]hex-2-enes 3a and c. 3a is easily converted into the 1.4-dihydropyridazine 5a. On the other hand the reaction of 1b with 2a directly affords the 1.4-dihydropyridazine 5b. The 2.3-diazabicyclo[3.1.0]hex-2-enes 3a and c isomerize to the allyl diazomethanes 4a and c on heating in benzene. In the case of the reactions 2b+1b as well as 6+1a the direct formation of allyl diazo compounds (4d and 8a respectively) is observed. In a novel reaction 9-diazofluorene (6) yields the 1.3-butadiene 9 when reacted with the cyclo-propene 1b.
Heterocyclische Siebenring-Verbindungen, XXX Synthese und Eigenschaften von 4-Methoxy-1,5-benzothiazepin, einem einfachen Vertreter des 1,4-Thiazepin-Ringsystems/ Heterocyclic Seven-Membered Ring Compounds, XXX Synthesis and Properties of 4-Methoxy-1,5-benzothiazepine, a Simple Derivative of the 1,4-Thiazepine Ring System
Authors: Hofmann Hans , Fischer Herbert
Published: March 2015

Alkylation of 1,5-benzothiazepin-4(5H)-one (1) with dimethyl sulfate and base yields the N-methyl compound 2 whereas with trimethyloxonium fluoroborate the lactimether 3, a simple derivative of the unknown, 1,4-thiazepine is obtained. Compound 3 eliminates sulfur on heating in toluene, yielding 2-methoxy-quinoline. Oxidation of 3 with peracid produces the stable 1,1- dioxide (4).
Reactivity of 1,1-DithioIato Ni(II) and Co(II) with Phenylthiourea, Chlorophenylthiourea and Bis(diphenylphosphinothioyl)methane
Authors: Aly Aref A. M. , Kamal Mostafa M. , El-Meligy Mahmoud S. , El-Said Asma I.
Published: March 2015

The following mixed ligand complexes were synthesized and characterized: Co(Phdtcz)2(Phtu)2, Co(Phdtcz)2(Clphtu)2 , Co(Phdtcz)2(dtm), Ni(Et2dtc)2(dtm), Ni(Phdtc)2(dtm), Ni(p-Toluiddtc)2(dtm), Ni(α-naphdtc)2(dtm), and Ni(Phdtcz)(Et2dtc); where Phdtcz = phenyldithiocarbazate, Et2dtc = diethyldithiocarbamate, Phdtc = phenyldithiocarbamate, p-Toluiddtc = p-toluidinedithiocarbamate, α-naphdtc = α-naphthyldithiocarbamate, Phtu = phenylthiourea, Clphtu - chlorophenylthiourea, and dtm - bis(diphenylphosphinothioyl)-methane. Electronic and IR spectra, magnetic, conductivity and X-ray powder diffraction measurements were carried out. The Ni(II) and Co(II) complexes are suggested to be square planar and octahedral, respectively. The biological activity of the complexes was also tested.
Ein weiteres P-Fluor-Ylid: [N(CH3)2]2PF=CH-CH(n-C4H9)-P[N(CH3)2]2 (4) Darstellung und NMR-Daten / A Further P-Fluoro-Ylide: [N(CH3)2]2 PF=CH-CH(n-C4H9)-P[N(CH3)2] 2 (4) Preparation and NMR Data
Authors: Heckmann Gernot , Neumüller Bernhard , Fluck Ekkehard
Published: March 2015

Preparation and properties of the title compound 4, [N(CH3)2]2 PF2-(CH2)2-PF2[N(CH3)2]2 (2), and [N(CH3)2]2
+PF-(CH2)2--PF5 (3), are described. The 1H, 19F, 31P, and 13C NMR spectra in double and triple resonance mode of 4 are recorded and discussed in detail. A 7J(HF) long-range coupling could be identified. 300 MHz-1H spectra show hindered rotation around the P-N bonds at room temperature
Gasphasen-Reaktionen, 58 [1, 2] β-Chlorethylazid: HCl-Eliminierung und Pyrolyse / Gas Phase Reactions, 58 [1, 2] β-Chloroethyl Azide: HCl Elimination and Pyrolysis
Authors: Bock Hans , Dammel Ralph
Published: March 2015

The HCl elimination from β-chloroethyl azide (1-azido-2-chloroethane) over potassium tert. butanolate at 350 K in a low pressure flow system is optimized using PE spectroscopic real-time gas analysis. The highly explosive vinyl azide formed can be purified by cool-trapping the by-products. Its subsequent and virtually hazard-free pyrolysis yields 2H-azirine, which can be isolated at temperatures below 240 K.

In contrast, the direct pyrolysis of β-chloroethyl azide requires temperatures above 710 K and results in a simultaneous split-off of both HCl and N2, yielding acetonitrile as the main thermolysis product. No intermediates such as β-chloroethanimine or ketenimine are observed, a result which is interpreted in terms of chemical activation
Beiträge zur Chemie des Phosphors, 174 [1] 1,3-Diaminotriphosphan(5), H2N-PH-PH-PH-NH2, ein neues Produkt der Spaltung von weißem Phosphor mit Natrium in flüssigem Ammoniak / Contributions to the Chemistry of Phosphorus, 174 [1] 1,3-Diaminotriphosphane(5), H2N-PH-PH-PH-NH2, a Novel Product of the Cleavage of White Phosphorus with Sodium in Liquid Ammonia
Authors: Baudler Marianne , Düster Doris
Published: March 2015

In the reaction of white phosphorus with sodium in liquid ammonia the hitherto unknown 1,3- diaminotriphosphane(5) (1) is formed besides other products. The composition and the structure of 1, which is only stable in liquid ammonia, have been elucidated by 31P NMR spectroscopy. Of the three possible diastereomers only the erythro,erythro-isomer 1a with transoid-oriented NH2 groups is present
Synthese und absolute Konfiguration kettenverzweigter, Cimetidin-analoger Thioether / Synthesis and Absolute Configuration of Chain Branched Cimetidine Analogous Thioethers
Authors: Elza Sigurd , Dräger Martin , Schunack Walter
Published: March 2015

Chain branched Cimetidine analogous thioethers, promising building blocks for the preparation of H2-histaminergic compounds, were synthetized from chiral aminoalkanethiols. Enantiomerically pure amino acids or aminoalcohols were used as starting materials. In one case, a resolution via neutral and acid di-O-(4-toluoyl)tartrates was achieved in good yields and satisfying enantiomeric excess. The absolute configuration of an ethyl branched compound was determined using X-ray diffraction and anomalous dispersion
Transformation of Some tRNA “Wobble Uridines” to their 2-Thioanalogues
Authors: Małkiewicz Andrzej J. , Nawrot Barbara , Sochacka Elżbieta
Published: March 2015

2′,3′-O-Isopropylidene-5-[(N-trifluoroacetyI)methoxycarbonylmethylaminomethyl]uridine (5) and 2′,3′-0-isopropylidene-5-ethoxycarbonylmethoxyuridine (6) have been prepared using as the substrates 2′,3′-O-isopropylidene-5-chloromethyluridine (11) and 2′,3′-O-isopropylidene- 5-hydroxyuridine (8). respectively. The transformation of 5 and 6 into respective 2,5′-anhydro-nucleosides 16 and 10 followed by treatment of 16 and 10 with liquid hydrogen sulphide/pyridine system produces 2′,3′-O-isopropylidene-5-[(N-trifluoroacetyl)methoxycarbonylmethylamino- methyl]-2-thiouridine (17) and 2′,3′-O-isopropylidene-5-ethoxycarbonylmethoxy-2-thiouridine (18). The acid catalysed methanolysis of 6 and 18 yields 5-methoxycarbonylmethoxyuridine (4) and its 2-thioanalogue 4a, while refluxing of 5 and 17 with 50% acetic acid gives 5-[(N-tri-fluoroacetyl)methoxycarbonylmethylaminomethyl]uridine (2) and its 2-thioanalogue 2a
Synthese und Molekülgeometrie von Dichloro[η2-bis(di-r-butylphosphino)methan]pIatin(II), Pt(dtbpm)Cl2. Die Elektronenstruktur von 1,3-Diphosphaplatinacyclobutan-Fragmenten / Synthesis and Molecular Structure of Dichloro[η2-bis(di-t-butylphosphino)methane]platinum(II), Pt(dtbpm)Cl2. The Electronic Structure of 1,3-Diphosphaplatinacyclobutane Fragments
Authors: Hofmann Peter , Heiß Helmut , Müller Gerhard
Published: March 2015

Based upon the experimentally known but yet unexplained very different reactivities of the two isoelectronic and isolobal intermediates Pt(PMe3)2 and Pt(PEt3)2, the electronic structure and bonding capability of such 14 electron fragments as a function of their geometry (P-Pt-P angle α, determined by the phosphane cone angle) are investigated using molecular orbital calculations. A decrease of the P-Pt -P angle leads to an exceptionally pronounced energy ascent of the b2-HOMO of Pt(PR3)2 species, which, as a consequence, might lead to unusual reactivity patterns and bonding capabilities of 1,3-diphosphaplatinacyclobutane fragments, for which an extreme electronic situation is enforced by steric constraints. Dichloro[η2-bis(di-r-butylphosphino) methane]platinum(II), Pt(dtbpm)Cl2, is synthesized as a potential precursor of Pt(dtbpm), in order to allow experimental investigations of this taylor made four-membered ring chelate complex of Pt(0). The crystal and molecular structure of Pt(dtbpm)Cl2 · 2 CHCl3 has been determined by X-ray diffraction.
On the Stereochemistry of the Lone-Pair Electrons in AX6E-Systems: Dynamically Distorted Anion in (NH4)2SeBr6, Statically Distorted Anion in 1,3-Propanediammonium-Hexabromoselenate(IV) (C3N2H12)SeBr6
Authors: Abriel Walter
Published: March 2015

Using 293 K diffractometer intensity data, the crystal structures of (NH4)2SeBr6 (1) and [H3N(CH2)3NH3]SeBr6 (2) have been determined by single crystal X-ray technique and refined to a final Rw of 0.049 and 0.040, respectively. The dark red crystals of 1 are cubic (space group Fm3m) with a = 10.478(2) Å and Z = 4. This structure contains SeBe6
2- octahedra (point symmetry m3̄m, distance Se-Br: 2.577(2) Å in an antifluorite type arrangement of cations and anions. In contrast, the SeBr fi 2-ion in 2 is statically distorted (approximate point symmetry 3m, distance Se-Br min. 2,547(2), max. 2.595(2) Å. The dark red crystals are orthorhombic (space group Pnma) with a = 17.795(3), b = 7.5037(6), c = 10.476(1) Å and Z = 4. The results agree with the rules for the appearance of a static/dynamic stereochemical effect of the lone pair electrons given for TeX6
2- (X = Cl, Br, I) species (W. Abriel, Acta Crystallogr. B 42, 449 (1986)). Consequently these rules can be extended considering SeX6
2- as well. Basic structural data for all compounds containing AX6
2- ions (A = Se, Te; X = Cl, Br, I) known to date are given including the ⊿-values (R. D. Shannon, Acta Crystallogr. A 32, 751 (1976)) as a measure for the distortion of the octahedral anion.
Oligophosphan-Liganden, XXIII. Synthese und Chemie des metallacyclischen Eisenkomplexes / Oligophosphine Ligands, XXIII. Synthesis and Chemistry of the Metallacyclic Iron Complex
Authors: Antberg Martin , Dahlenburg Lutz
Published: March 2015

The complex

(1) was obtained by reduction of FeCl2[P(CH2CH2CH2PMe2)3] with lithium dust in tetrahydrofuran at room temperature. Although an equilibrium of 1 with its iron(0) tautomer Fe[P(CH2CH2CH2PMe2)3] could not be detected by NMR spectroscopy, the coordinatively unsaturated 16e-fragment could be trapped by ligands favouring low oxidation states: trimethyl phosphite reacted with 1 to give Fe[P(OMe)3][P(CH2CH2CH2PMe2)3] (2), whereas carbon monoxide was observed to add to the metal(O) species to yield a mixture of Fe(CO)[P(CH2CH2CH2PMe2)3] (3) and

-(CH2)3-PMe2 (4). 1 was completely unreactive towards dihydrogen and dinitrogen, not, however, towards carbon dioxide, which was found to insert into both the Fe-H and Fe-C bond producing

(5). Methyl and benzyl iodide interacted with 1 to give the iodo derivative

(6). The reaction of 1 with methanol lead to FeH2[P(CH2CH2CH2PMe2)3] (7).
Examination of a New Cross-Linker in Monoclonal Antibody Reaction Against the C-Terminus of Tobacco Mosaic Virus Coat Protein
Authors: Dietzgen Ralf G. , Sander Evamarie , Christner Jürgen , Jung Günther
Published: March 2015

The C-terminal tetrapeptide Gly-Pro-Ala-Thr of TMV coat protein was linked to poly- (L-lysine) of 37,300 and 80,000 daltons and to human serum albumin using different ratios of tetrapeptide to carrier. The new hydrazidosuccinyl HSc cross-linker effected the specific amino terminal attachment of the tetrapeptide by azide coupling. The synthetic peptide and its conjugates were controlled by various methods including 13C NMR and CD. Using a conjugate containing 74 tetrapeptide residues linked to poly(L-lysine) of 80,000 daltons for screening of monoclonal antibody by ELISA, 5.8 fmol of peptide were detectable.

The serological and biological properties of the monoclonal antibody were assayed by indirect ELISA and by quantitative determination of virus neutralization. This neutralization could be reversed by the poly(L-lysine)-tetrapeptide conjugate but not by the free tetrapeptide.
Darstellung und Eigenschaften von und Reaktionen mit metallhaltigen Heterocyclen, LVII [1]. Stabilisierung der RPSR′-Gruppe in der Koordinationssphäre von Carbonylmangan-Komplexen / Preparation and Properties of, and Reactions with Metal-Containing Heterocycles, LVII [1]. Stabilization of the RPSR′ Group in the Coordination Sphere of Carbonylmanganese Complexes
Authors: Lindner Ekkehard , Auch Konrad , Hiller Wolfgang , Fawzi Riad
Published: March 2015

Stabilization of RPSR′, Manganese Complexes, X-Ray Stabilization of a RPSR′ function is possible by its incorporation into the mono-and binuclear manganese complexes, t-BuP[Mn(CO)5]SPh (3b) and (μ-CH3PSPh)(μ-SPh)Mn2(CO)8 (4a), re-spectively. Formation of 4a is accomplished via the precursors 3a and PhSMn(CO)5 (5), which are both unstable. 3a, b and 5 are formed by reaction of RP(Cl)SPh (la, b) [R = CH3 (a), t-Bu (b)] with [Mn(CO)5]- (2). 4a crystallizes in the orthorhombic space group Pbca with Z = 8.
The Interaction of Copper(II) Ions with the Thyrotropin-Releasing Hormone Synthesized by Adpoc Protection
Authors: Maskos Karol , Kaibacher Hubert , Stock Wieland , Voelter Wolfgang
Published: March 2015

Thyrotropin-Releasing Hormone (TRH), Copper(II) Ion Complexes The copper(II) complexes of the thyrotropin-releasing hormone (L-pyroglutamyl-L-histidyl-L-prolinamide, TRH) in 3 M LiCl-water solutions were investigated as a function of pH by circular dichroism, absorption, and electron spin resonance spectroscopy. It was concluded that a simple ML (IN) complex of copper(II)-TRH is formed over the pH range 4.0-4.5, while 2N and 3N complexes are present in the solutions of pH 4.4-6.0. From pH 6.1 to 9.8 an ML2 (4N) complex is formed and this species is the only complex found over the pH range 6.5-8.5. At pH values above 9.0 a 3N species is formed in addition to a 2N complex which is present in the solutions of pH 11.3. These observations are controversial to former reports.

TRH [1-2] was synthesized using the fully Adpoc (adamantyl-isopropyloxycarbonyl)-protected histidine. From the synthesis the advantages of the Adpoc group, cleavable under extreme mild acidolytic conditions, become obvious.
Studies on the Peptide Alkaloids of Discaria febrifuga
Authors: Voelter Wolfgang , Morel Ademir Farias , Atta-ur-Rahman  , Qureshi Muhammad Munawer
Published: March 2015

A new tryptophan-containing peptide alkaloid, “discarin-K”, has been isolated from Discaria febrifuga, a shrub growing in Brazil, Argentina and Uruguay. Its structure has been determined as 1 on the basis of spectral studies. Another peptide alkaloid, franganin, was also isolated from the same plant and its 1H NMR and 13C NMR have been studied using COSY-45, 2 D-J resolved and DEPT techniques.
Struktur und Reaktivität von isoanellierten heterocyclischen Systemen mit Anπ- und (4n+2)π-Elektronen, XII [1]. 2-tert-Butyl-4-methyl-2,4-dihydropyrrolo[3,4-b]indole: Tricyclische Hetarene mit isoanellierten Pyrrolringen / Structure and Reactivity of Isoannelated Heterocyclic Systems with 4nπ- and (4n+2)π-Electrons, XII [1] 2-terr-Butyl-4-methyl-2,4-dihydropyrrolo[3,4-b]indoles: Tricyclic Hetarenes with Isoannelated Pyrrole Rings
Authors: Kreher Richard P. , Dyker Gerald
Published: March 2015

2-tert-Butyl-4-methyl-2,4-dihydropyrrolo[3,4-b]indole (4a) has been prepared via selective reduction of 2-rm-butyl-4-methyl-2,4-dihydropyrrolo[3,4-b]indol-l(2H)-one or -3(2H)-one 5 and 6 with diisobutylaluminiumhydride. The same precursors 5 and 6 can be transformed into 2-tert-butyl-4-methyl-2,4-dihydropyrrolo[3,4-b]indoles (4b) and (4c) bearing a methoxy group in 1- or 3-position via a two step procedure consisting in O-alkylation and CH-deprotonation. NMR Investigations afford an insight into the structure of the stable tricyclic hetarenes.
Acylierungsreaktionen an Enaminen / Acylation Reactions of Enamines
Authors: Möhrle Hans , Dwuletzki Heinz
Published: March 2015

The ratio of isomeric enaminones, obtained by acylation of enamines with acid chlorides in the presence of triethylamine, depends on the possibility of forming isomeric enoles of the inter-mediate cyclobutanone adducts.
Efficient Syntheses of a New Class of 6-Amino-6-deoxy Sugars
Authors: Malik Abdul , Ahmed Zaheer , Kazmi Najam-ul-Hussain , Khan Abdul Qasim
Published: March 2015

Amino Sugars, Triflate Displacement, Amino Acids Novel one step syntheses of a new class of phar-macologically interesting 6-amino-6-deoxy sugars are described. The reaction sequence consists of esterifying 1,2:3,4-di-O-isopropylidene-α-D-galac-topyranose with trifluoromethanesulfonic anhydride and reacting the resulting triflate with a variety of suitably protected naturally occurring amino acids. The difficulties which, sometime, are encountered during displacement reactions in carbohydrates are absent.
Stickstoffverbindungen von Elementen der dritten Hauptgruppe mit intra- und intermolekularen Donor-Akzeptor-Bindungen, III [1]. Dynamische Phänomene und Lewis-Säure-Stärke / Nitrogen Compounds of Elements of the Third Main Group with Intra- and Intermolecular Donor Acceptor Bonds, III [1]. Dynamic Phenomena and Lewis Acidity
Authors: Veith M. , Belo A.
Published: March 2015

Compounds of the general formula tBuN(H)-SiMe2 -N(tBu)ElX2 (El = B, X = Me (1m), F (1f), Cl (1c); El = AI, X = Me (2m), Cl (2c), Br (2b); El = Ga, X = Me (3m), Cl (3c), Br (3b); El = In, X = Me (4m), Cl (4c), Br (4b); El = Tl, X = Me (5m)) and tBuN(D)-SiMe2-N(tBu)ElMe2 (El = Al (2d), Ga (3d), In (4d)) have been characterized by IR and temperature dependent 1H NMR techniques with respect to their structural changes in solution. A reversible, dynamic, intramolecular equilibrium between two enantiomeric four-membered rings has been established to be responsible for the changes in the spectra. The cyclic form B1, which arises from Lewis acid base interaction of the tert-butyl-amino with the ElX2 group, transforms to the mirror-image B2 via an acyclic intermediate, in which reorientation of the groups by rotation or inversion can take place. In the boron derivatives (1m, 1c, and 1f) no comparable N-B interaction can be detected. The Lewis acidity of the ElX2 group deduced from NH wave numbers increases within the following series: TlMe2<GaMe2≈InMe2<AlMe2<GaBr2≈InBr2<GaCl2≈AlBr2≈InCl2<AlCl2. Intramolecular hydrogen transfer from one nitrogen atom to the other can be excluded by comparison of the rate constant kʜ vs. kᴅ. The free enthalpy of activation Δ G* depends on the acidity of E1X2, the steric requirements and the relative masses of X. The syntheses and characterisation of 1f, 2b, 3b, 4b, 2d, 3d, and 4d are described.
PH-funktionelle Phosphane mit α- und β-ständigen 2-Pyridylsubstituenten 2-C5H4N—[CH2]n—PRH (R = H, iPr, tBu, Ph, 2-C5H4N-[CH2]n; n = 1, 2) / PH-Functional Phosphanes with 2-Pyridyl Substituents in α- or β-Position 2-C5H4N —[CH2]n—PRH (R = H, iPr, tBu, Ph, 2-C5H4N-[CH2]n; n = 1,2)
Authors: Spiegel Gerd U. , Stelzer Othmar
Published: March 2015

PH-functional phosphanes containing a 2-pyridyl substituent in α- or β-position to phosphorus, e.g. 2-C5H4N - [CH2]n-PRH (R = H, iPr, tBu, Ph; n = 1,2) have been obtained. The reactivity of the PH-groups can be employed for the synthesis of tridentate NPN-hvbrid donors. [2-C5H4N -CH2-CH2]2PR (R = H. Ph). The phosphanes 2-C5H4N-[CH2]n-PRH behave as monodentate ligands in transition metal complexes and form labile chelate ring systems. They may bridge metal-metal bonds to form seven membered ring systems, e.g. Mo2PC3N. The coordination of the N-donor of the ligands 2-C5H4N - [CH2]n-PRH to a transition metal atom is indicated by a lowfield shift and a small 31P - 13C-splitting of the 13C{1H} NMR signal of carbon atom 6 in the pyridin ring system.
Synthese und Absolute Konfiguration von (+)-1-Amino-2-propanthiol·HCl / Synthesis and Absolute Configuration of ( + )-1-Amino-2-propanethiol · HCl
Authors: Elz Sigurd , Dräger Martin , Sattler Hans-Joachim , Schunack Walter
Published: March 2015

)-4a-

The structure of (-)-5-methyl-2-phenylthiazolidine (( -)-4a), an intermediate in the synthesis of (+)-1-amino-2-propanethiol · HCl ((+)-2 · HCl), was elucidated by 1H and 13C NMR spectroscopy. In contrast to earlier findings it was shown that the important intermediate ( -)-4a is not a single diastereomer but represents a 1:1 mixture of (2R,5Sand ((2S,5S)-4a-diastereomers. The absolute configuration of the (2S,3S)-di-O-(4-toluoyl)tartrate of the disulfide (5) derived from (+)-2 · HCl was determined to be (S,S) using X-ray technique.
Chemie an starren Grenzflächen, 7 [1] Ausgewählte Beispiele der chemischen Grenzflächenmodifizierung von Aerosil / Chemistry at Rigid Surfaces, 7 [1] Selected Examples of the Chemical Surface Modification of Aerosil
Authors: Horner Leopold , Ziegler Hans
Published: March 2015

Aminoaerosil containing primary amino end groups is obtained according (1) by reaction of aerosil with γ-triethoxysilylpropyl amine (Table II).

The NH2-anchor groups are acylated in the usual manner: carbonic acid anhydrides, acid chlorides and acid azides and by application of the carbodiimide method (Table III). Optically active groups and phosphoric acid diestergroups are covalently linked with the surface of aerosil according (2) and (3). Aminoaerosil reacts with vinylsulfones as anchor groups of dyes (Remazol- Dyes) producing a covalent bond according (6).

Functional groups linked to the surface of aerosil react “normal” (with respect to homogenous solutions) with group specific reagents. Examples: bromination, ozonization of C-C double bonds, hydrolysis of phosphoric acid esteramidates and surface bound chloroamine-T groups. "Interparticular" reactions of modified aerosil are not observed. But aerosil with electroactive groups are electroreduced using Hg- or Pb-electrodes.

The optical induction of the catalytic hydrogenation of prochiral defines using palladium deposited on chiral modified aerosil surfaces is low (ca. 1%).

Some analytical methods are presented, which are recommended for the determination of the amount of functional groups bound to the surface.
Darstellung und Kristallstrukturen von [Co6Se8(PPh3)6]+[CoCl3(THF)]- , [Co8Se8(PPh3)6][Co6Se8(PPh3)6] und [Co8Se8(PPh3)6]+[CoCl3(PPh3)]-
Authors: Fenske Dieter , Ohmer Johannes , Merzweiler Kurt
Published: March 2015

(NBu4)[CoCl3(PPh3)] reacts with Se(SiMe3)2 to form the new clusters [Co8Se8(PPh3)6][CoCl3(PPh3)] (6) and [Co8Se8(PPh3)6][Co6Se8(PPh3)6] (7). The structures of 6 and 7 have been determ ined by X-ray diffraction. 6 and 7 crystallize in the space group P1̄ with two formula units per unit cell and with the following lattice constants at 180 K: 6: a = 1413.8(10), b - 2224.2(23), c = 2348.4(17) pm, α = 86.06(5), β = 86.58(5), γ = 76.11(5)°; 7: a = 1465.9(4), b = 1627.6(6), c = 2505.7(6) pm, α - 98.69(2), β = 96.23(2), γ = 113.06(2)°. The cluster structures of the [Co8Se8(PPh3)6]n (n = 0, 1 +) depend on the total number of electrons in the cluster units.
Darstellung von monomerem Methylenaminoacetonitril H2C = N —CH2—CN in der Gasphase [1]
Authors: Dammel Ralph , Bock Hans
Published: March 2015

The reactive intermediate methyleneaminoacetonitrile H2C = N - C H2 - CN has been generated via thermal retrotrimerization of N ,N',N"-tris(cyanomethyl)hexahydro-s-triazine and characterized by its photoelectron, mass and low-temperature NMR spectra. A fully geometryoptimized MNDO calculation allows to assign the observed ionization energies and yields estimates for other molecular properties, e.g. a rather high dipole moment.
Die Struktur von Undecacarbonyl-(μ-trifluormethylisocyanid)trieisen Fe3(μ-CNCF3)(CO)11 in Lösung
Authors: Lentz Dieter
Published: March 2015

According to its 13C NMR spectra, undecacarbonyl-(μ-trifluorom ethylisocyanide)triiron, Fe3(μ-CNCF3)(CO)11 , is only partly nonrigid in solution even at ambient temperature. However, on cooling to -100 °C the molecule is rigid on the NMR time scale.
Der elektronisch stabilisierende Beitrag des Ph3P=N-Liganden. Darstellung von CH3WCl4N =PPh3 und das elektrochemische Verhalten von Ph3PN-substituierten Wolfram(VI)-Halogeniden
Authors: Roesky Herbert W. , Tojo Tetsuro , Ilemann Michaela , Westhoff Dieter
Published: March 2015

The reaction of CH3WCl5 and Me3SiN = PPh3 yields CH-3WCl4N = PPh3 (1). The electrochem ical reduction of 1, F5WN = PPh3 (2) and F4W (N = PPh3)2 (3) has been investigated using cyclic voltammetry and potentiostatic methods. The cyclic voltammogram of 1 shows two reduction waves at Ef + 1.72 and 0.420 V. The controlled potential reduction of 1 indicates two steps of reversible one-electron charge transfers. The cyclic voltammograms of 2 and 3 in CH2Cl2 show reversible one-electron waves at Ef -0.45 and -1.45 V, respectively. The reduced products were analyzed by 19F and 31P NMR spectroscopy.
tert-Butylimino-cyclopentadienyIvanadiuni(V)-Verbindungen Darstellung, Struktur und NMR-spektroskopische Untersuchungen
Authors: Preuss Fritz , Becker Harald , Häusler Hans-Joachim
Published: March 2015

The cyclopentadienyl compounds tC4R9N = VCpCl2 (2). tC4H9N = VCp(OtC4H9)Cl, tC4H9N = VCp(OtC4H9)(R) (R = CH3, "C4H9, CH2SiMe3), tC4H9N = VCp2(OtC4H9) (5) and ,tC4H9N = VCp(OtC4H9)2 have been prepared starting from tC4H9N = VCl3
1H and 51V NMR spectra are discussed; except for 5, the C5H5 rings are η5-coordinated to the metal atom. The temperature dependence of the 1H NMR spectrum of 5 indicates two types o f intramolecular rearrangements: η1/η5-Interchange of the C5H5 rings and fluxional behavior of the η1-C5H5 ring. The molecular structure of 2 has been investigated by X-ray diffraction analysis.
Übergangsmetallkomplexe instabiler Ylide, X [1] Chemische und elektrochemische Untersuchungen zu den Redox-Eigenschaften cyclischer Tetracarbonylchrom-Ylidchelatkomplexe / Transition Metal Complexes of Unstable Ylides, X [1] Chemical and Electrochemical Investigations of the Redox Properties of Cyclic Tetracarbonylchromium-Ylide-Chelate-Complexes
Authors: Weber Lothar , Lücke Ewald , Kölle Ulrich , Ohst S.
Published: March 2015

Treatment of the ylide chelate complexes (CO)4

(1) with (C5H5)2Fe+PF6
- leads to the organometallic radical cations 2. The oxidation process of 1 is also checked electrochemically by means of cyclovoltammetry, which exhibits a reversibel one electron oxidation between -0.1 and +0.3 V vs. SCE. These potentials are more negative than in any other complex of the general type Cr(CO)4L2 (L e.g. = PR3, CNR).
Zur Azulen-Azulen-Umlagerung des 1-Phenylazulens
Authors: Wetzel Arthur , Zeller Klaus-Peter
Published: March 2015

1-Phenyl-[3-13C]- (8) and 1-phenyl-[4-13C]azulene (19) are prepared using ethyl [2-13C]acetate and [formyl-13C]dimethylformamide as 13C-sources. The thermal azulene-azulene rearrangement of 8 and 19 yields 2-phenyl-[3a-13C]azulene and 2-phenyl-[4-13C]azulene, respectively. In com bination with earlier results it is concluded that in the skeletal rearrangement the carbon atoms of the five-m em bered ring are shifted by one position, whereas the carbon atoms C-4-C-8 of the seven-membered ring remain at their original position.
Oxidative Addition von H2 und HCl an Iridium-Schwefelmonoxid- und Schwefeldioxid-Komplexe/ Oxidative Addition von H2 und HCl an Iridium-Schwefelmonoxid- und Schwefeldioxid-Komplexe
Authors: Schenk Wolfdieter A. , Leißner Johanna
Published: March 2015

Square planar iridium(I) complexes of sulfur monoxide and sulfur dioxide undergo oxidative addition with dihydrogen and hydrogen chloride. The resulting hydrido-iridium(III) complexes have been characterized by 1H , 31P NMR and IR spectroscopy. The limited stability of the sulfur monoxide derivatives is explained as resulting from decreased back-bonding between iridium and sulfur.
Reaktive E = C (p—p) π -Systeme, XI. Hydrometallierungsreaktionen des Perfluor-2-phosphapropens F3CP = CF2/ Reactive E = C (p —p) π -Systems, XI. Hydrometallation Reactions of Perfluoro-2-phosphapropene F3CP = CF2
Authors: Grobe Joseph , Le Van Duc , Nientiedt Jürgen
Published: March 2015

The reactions of F3CP = CF2 (1) with Me3GeH, Me3SnH, and (C5R5)(CO)3MH (M = Cr. Mo, W; R = H , Me) proceed via addition to the PC double bond yielding tertiary phosphanes of the type Me3M′P(CF3)CF2H[M′ = Ge (2), Sn (3)] or (C5R5)(CO)3MP(CF3)CF2H [R = H; M - Cr (6), Mo (7). W (8); R = Me; M = Mo (9), W (10)]. 2 and 3 are labile compounds, which decompose by elimination of Me3M′F , a reaction which in the case of 3 has been used to prepare the new phosphaalkene F3CP = C(H)F (5) and its [2+4]-cycloaddition product 4 with 2.3-dimethyl-1.3- butadiene. The H substituent (instead of F) in 5 and its derivatives has a surprising influence not only on the stability of the compounds but also on their spectroscopic data, as shown by com parison with 1 and derivatives of the type Me3M ′P(CF3)2 and (C5H5)(CO)3MP(CF3)2. respectively. New compounds are characterized by NMR, MS. GC/MS and IR measurements.
1-O-(13-Methyl-1-Z-tetradecenyl)-2-O-(13-methyItetradecanoyl)- glycero-3-phospho-ethanolamin, ein Plasmalogen aus Myxococcus stipitatus/ 1-O-(13-Methyl-1-Z-tetradecenyl)-2-O-(13-methyltetradecanoyl)-glycero-3-phosphoethanolamine, a Plasmalogen from Myxococcus stipitatus
Authors: Stein J. , Budzikiewicz H.
Published: March 2015

The structure of 1-O-(13-methyl-1-Z-tetradecenyl)-2-O-(13-m ethyltetradecanoyl)-glycero- 3-phospho-ethanolamine isolated from Myxococcus stipitatus has been elucidated. 1H and 13C NMR as well as mass spectral data have been accumulated which allow a ready identification and structure elucidation of compounds of this type.
Molecular Determinants for Drug Receptor Interactions, 9 1H and 13C NMR Spectra of the Narcotic Antagonist N-Allyl-N-normetazocine by Two-Dimensional Chemical Shift Correlation Spectroscopy
Authors: Perly Bruno , Le Bail-Richer Patricia , Pappalardo Giuseppe C. , Grassi Antonio
Published: March 2015

The high frequency 1H and 13C NMR spectra (at 500 and 75.47 MHz, respectively) of N-allyl- N-normetazocine (NAM) hydrochloride in 2H2O solution were run and fully analyzed with the aid of both homonuclear 1H -1H and heteronuclear 13C - 1H chemical shift correlation experiments. Selective broadening of the signals of the protons in 3-, 4-, 8-, 9-, 12-positions was observed at temperatures <350 K. This was found to be consistent with an inversion process occurring between the N-equatorial and N-axial configurational isomers of NAM whose rate of exchange is of the same order of magnitude of the chemical shifts differences at 500 MHz. The increase of temperature at 350 K is thus adequate to make “fast” the process in the NM R time scale and then to resolve the spectral portions.

The experimental proton-proton coupling constants were found to be consistent with a slightly distorted chair conformation of the piperidinic ring in NAM hydrochloride.

The 13C NMR spectrum showed the distinct spectra of the two conformers, which are present in the ratio of ca. 80 (N-equatorial) : 20 (N -axial). The field frequency employed for the experiment was therefore sufficient to make “slow” the exchange process between the two isomeric forms, whose resonance peaks could be isolated in the non-acidified solution.
Notizen: Versuche zur Herstellung eines Alkenyl(dimethyl)zinnhydrids: Gibt es eine intramolekulare Sn–H–B-Brücke?/ Attempts at the Synthesis of an Alkenyl(dimethyl)tin Hydride: Is there an Intramolecular Sn–H–B Bridge?
Authors: Kerschl Susanna , Wrackmeyer Bernd
Published: March 2015

2-(E)-Dim ethyl(chloro)stannyl-3-diethylboryl-2- pentene (lc) reacts with trimethyltin hydride (3) to give the corresponding alkenyl(dim ethyl)tin hydride (2). Compound 2 has been characterized by 1H, 11B, 13C, 119Sn NMR . Neither the NMR nor the IR data are in support of an intramolecular Sn-H-B bridge.
Speicherung des labilen Silaethens Me2Si=C(SiMe3)2 mit N-Trimethylsilyl-benzophenonimin Ph2C=NSiMe3 / Storing of the Labile Silaethene Me2Si=C(SiMe3)2 with N-Trimethylsilyl-benzophenoneimine Ph2C=NSiMe3
Authors: Wiberg Nils , Preiner G. , Wagner G. , Köpf H. , Fischer G.
Published: March 2015

N-Trimethylsilyl-benzophenoneimine Ph2C=NSiMe3 is able to “store" the silaethene Me2Si = C(SiMe3)2 (1). produced from Me2SiF-CLi(SiMe3)2, under formation of a [2+4]- and [2+2]-cycloadduct (2, 3), respectively. Above 60 °C (above 120 °C) 2 or 3 by the way of 1 transform into a 1:5 mixture of 2 and 3 (into a 1:1 mixture of the dimer of 1 and the insertion product of 1 into the SiN-bond of Ph2C=NSiMe3). In the presence of 2,3-dimethyl-1.3-butadiene (dmb), 2 or 3 form by way of the reaction of the intermediate 1 with dmb a [2 + 4]-cycloadduct (75%) and an ene reaction product (25%). The rate constants of the first order decomposition of 2 or 3 in the presence of dmb (80 °C. solvents like Et2O, Q6H6 are in the order of 2x10-4s-1 (τ1/2ca. 1 h) and 3x10-
5s-1 (τ1/2 ca. 6 h). respectively.
Reaktivität des labilen, durch Adduktbildung mit Ph2C=NSiMe3 gespeicherten Silaethens Me2Si=C(SiMe3)2 / Reactivity of the Labile Silaethene Me2Si = C(SiMe3)2, Stored as Ph2C =NSiMe3 Adducts
Authors: Wiberg N. , Preiner G. , Wagner G. , Köpf H.
Published: March 2015

Silaethene Me2Si = C(SiMe3)2 (1), stored as Ph2C=NSiMe3 adducts and regenerated from the adducts at about 100 °C as a reaction intermediate, combines with reactants a-b (e. g. HO-H, RO-H. RCOO-H, RS-H. RHN-H, Ph2CN-H, RO-SiR3, R2N-SiR3, Ph2CN-SiR3, Cl-GeR3, Cl-SnR3) with insertion into the a-b bond, with a=b (e.g. 0 = CPh2, Me3SiN = CPh2, CH2=CHOMe, cis-piperylene), a=b=c (e.g. RN = N = N, O = N=N). a=b-c=d (e.g. butadiene, isoprene, trans-piperylene, 2,3-dimethylbutadiene, cyclopentadiene, anthracene, benzophenone, N-trimethylsilylbenzophenoneimine) under [2+2]-, [2+3]- as well as [2+A]-cycloaddition and with a=b-c-H (e.g. propene, butenes, isoprene. 2.3-dimethylbutadiene, acetone) under ene reac­tion. According to relative reaction rates, insertion and [2+2]-cycloadditions seem to proceed in two reaction steps, whereas [2+4]-cycloadditions and ene reactions with organic dienes and enes obviously are one step reactions. For relative reactivities cf. Table I.
[Ba(en)4]2 As4Te6, das erste Telluridoarsenat / [Ba(en)4]2 As4Te6, the First Telluridoarsenate
Authors: Eisenmann Brigitte , Zagler Roland
Published: March 2015

The new compound [Ba(en)4]2As4Te6 has been prepared by reaction of appropriate mixtures of the elements in dry ethylenediamine. It crystallizes in the monoclinic system, space group P21/n with a = 1776.0(6) pm, b = 1459.9(6) pm, c = 1000.0(4) pm, β = 101.8(1)°. The As4Te6
4- anion forms a six-membered ring As4Te2 of chair conformation, in which two As-As groups are bridged by Te atom s. A t each As atom a further exocyclic Te neighbour is bonded in the equatorial position. The Ba2+ cation is eight-coordinated by the bidentate ethylenediamine ligand.
Darstellung und Charakterisierung einfacher α-Sila- und α,ω-Disilaalkane als Vorstufen für die CVD-Erzeugung von amorphem Silicium a-SiC:H / Synthesis and Characterization of Simple α-Sila- and α,ω-Disilaalkanes: Precursors for the CVD Production of Amorphous Silicon a-SiC:H
Authors: Schmidbaur Hubert , Dörzbach Cornelia
Published: March 2015

Preparative methods have been explored for the synthesis of small, volatile polysilaalkanes, which could serve as starting materials for the production of amorphous silicon a-SiC:H. High yield pathways have been developed for H3SiCH2CH2SiH3 and H3SiCH2CH2CH2SiH3. These compounds can be converted into symmetrically halogen-functional derivatives through the reac­tions with SnCl4 or Br2. The homologous H3SiCH2CH2SiH2CH3 has also been prepared and halogenated, starting from the corresponding vinylsilane via the hydrosilylation route. Allylsilanes were the source of the synthesis of H3SiCH2CH=CH2, CH3SiH2CH2CH=CH, SiH2(CH2CH = CH2)2, SiH2(CH2CH2CH2SiH3)2, or HSi(CH2CH2CH2SiH3)3. Methylated deriva­tives are also available. - Some physical and spectroscopic properties of the new compounds have been investigated. In particular. NMR data were collected and used for an assessment of structure and isomerism.
Synthese und Kristallstruktur von (PPh4)2[Mo2(O2C—Ph)4Cl4] · 2 CH2Cl2, einem Komplex mit Mo≡Mo-Bindung / Synthesis and Crystal Structure of (PPh4)2[Mo2(O2C —Ph)4Cl4] ·2 CH2Cl2, a Complex with Mo≡Mo Bonding
Authors: Jansen Kay , Dehnicke Kurt , Fenske Dieter
Published: March 2015

The title compound has been prepared from (PPh4)2[Mo2(O2C-Ph)4Cl2] and CCl4 in CH2Cl2 solution as moisture sensitive crystals, which are black in reflexion and yellow in transmission. (PPh4)2[Mo2(O2C-Ph)4Cl4] · 2 CH2Cl2 was characterized by a X-ray crystal structure determination (7873 observed independent reflexions. R = 0.048). It crystallizes in the space group P1̄ with one formula unit in the unit cell; the lattice constants are a = 1186.4; b = 1404.0; c = 1451.0 pm; α = 61.98°; β = 78.91°; γ = 78.26°. The structure consists of PPh4
⊕ ions. CH2Cl2 molecules and centrosymmetric anions [Mo2(O2C-Ph)4Cl4]2⊝ containinga molybdenum d3 d3 unit with a relatively long Mo=Mo bond of 249.6 pm. The Mo≡Mo group is spanned in a chelate manner by four O atoms of two benzoate groups and by two further single O atoms of two further benzoate groups. Two terminal Cl atoms on each Mo atom complete the pentagonal bipyramidal coordination spheres about the Mo atoms.
Die Kristallstruktur von Mangantetrafluorid The Crystal / Structure of Manganese Tetrafluoride
Authors: Müller Bernd G. , Serafin Michael
Published: March 2015

Single crystals of dark blue MnF4 have been obtained by high pressure fluorination (pF2 = 3 kbar) of MnF2. There exist two modifications: α-MnF4 crystallizes tetragonally body centered with a = 12.63(1), c = 6.049(5) Å, space group I41/a-C4h
6 (No. 88). Z = 16; the structure of β-MnF4, (probably) rhombohedral with a = 19.56(2). c = 13.00(1) Å, Z = 72, is yet unknown in detail. MnF4 is paramagnetic with ,μeff (301.2 K) = 3.87 B. M. . The Curie-Weiss law is obeyed down to 22.4 K; the Madelung Part of lattice energy (MAPLE) is calculated to be 2475 kcal/mol.
Oligophosphan-Liganden, XXIV. Tris(2-dimethylphosphinophenyl)phosphan, P(C6H4PMe2-2)3 / Oligophosphine Ligands, XXIV. Tris(2-dimethylphosphinophenyl)phosphine, P(C6H4PMe2-2)3
Authors: Werner Detlef , Dahlenburg Lutz
Published: March 2015

Reaction of 2-BrC6H4PCl2 (1) with methyl lithium gave 2-BrC6H4PMe; (2). Metalation of 2 with n-butyl lithium and further reaction of the lithio-derivative 2-LiC6H4PMe2 with triphenyl phos­phite yielded the title compound. P(C6H4PMe2-2)3 (3). characterized by NMR and mass spectro­scopy as well as by an X-ray structure analysis. Quaternization of 2 with methyl iodide gave [2-BrC6H4PMe3]I (2a). the molecular structure of which has also been determined by single­crystal diffraction methods.
Bisdisubstituierte aromatische Phosphane als Komplexliganden / Bisdisubstituted Aromatic Phosphanes as Ligands for Metal Complexes
Authors: Schmitt Georg , Pritzkow H. , Latscha H. P.
Published: March 2015

The photochemical reaction of o-C6H4(PR2)2; R = OCH3, OC2H5 , m-C6H4(PR2)2; R = N(CH3): and p-C6H4(PR2)2; R = OCH3. N(CH3)2 with (tricarbonylj(methylcyclopentadienyl)- manganese (Cp')Mn(CO)3 (6) and p-C6H4(P(N(CHO3)2)2)2 with (tricarbonyl)(methyl)(cyclopenta- dienyl)molybdenum (CH3)(Cp)Mo(CO)3 (7) yields new manganese and molybdenum complexes. o-Phenylen-bis(phosphonousaciddimethylester)(carbonyl)(methylcyclopentadienyl )manganese (8) forms yellow crystals, whose structure is reported. The reaction of o-C6H4(P(OCH3)2)2 (1) with NiCl2 gives a 1:1 phosphane complex (14). Ni(OH)Clopm. The complexes are characterized by elemental analysis, 1H NMR, 31P NMR, IR and mass spectroscopy.
Molecular Complexes of Cyclophanes, Part XVII Charge-Transfer Complexes of [2.2]- and [2.2.2]Paracyclophane-carbamates with π-Acceptors
Authors: Mourad Aboul-fetouh E. , Lehne Verena
Published: March 2015

Charge-transfer (CT) complexation between some [2.2]- and [2.2.2]paracyclophane-carbamates as donors with 2,3-dichloro-5.6-dicyanobenzoquinone (DDO ) as well as tetracyanoethylene (TCNE) as π-acceptors has been evidenced by VIS. 1H NMR and IR spectroscopy. The site of interaction in the two different donor systems was determined. The results reveal no contribution of the nitrogen lone pair electrons of the carbamate functional group in the CT complexation. and the interaction is mainly of π-π* type. In addition, the existence of the transannular electronic interactions in [2.2]paracyclophane derivatives is responsible for CT complex formation.
Photochemistry of Pesticides, 12. On the Photoconversion of 1,3-Dihydro-2H̠-benzimidazole-2-thione, 2(3H̠)-Benzothiazolethione, and 2-Chlorobenzothiazole
Authors: Abdou W. M. , Sidky M. M. , Wamhoff H.
Published: March 2015

The photoreactivity of 1,3-dihydro-2H̠ -benzimidazole-2-thione ( 1a ) and 2(3H )-benzothiazolethione ( 1b ) has been studied in several solvents in the presence of oxygen with or without methylene blue as a sensitizer. The corresponding disulfides (5a, b), 2-oxo derivatives (2 a , b), benzimidazole and benzothiazole (11a, b), and elem ental sulfur have been characterized as the main products. The UV irradiation of the disulfides 5a , b results in the formation of the same product pattern as the thiones 1 a , b. Photolysis of 2-chlorobenzothiazole (12) in acetonitrile gives a mixture of 2 b , 2,2'-dibenzothiazole (13). while photolysis of 12 in ethanol yields 2b and 11 b . Products and mechanisms are discussed and compared with previous studies in this area.