bluuebunny/crossref_metadata_2025 huggingface dataset:
Zum Ligandeinfluß in neuen Ni(0)-Komplexen disubstituierter Butadiine / On the Influence of Ligands in New Ni(0) Complexes of Disubstituted Butadiynes
Authors: Rosenthal Uwe , Pulst Siegmar , Arndt Perdita , Baumann Wolfgang , Tillack Annegret , Kempe Rhett
Published: February 2015

It has been shown that disubstituted butadiynes react with L2Ni(C2H4) to yield mononuclear complexes L2Ni(η2(1:2 )-RC≡C -C ≡CR) (L = o-Tol-O)3P, R = SiMe3 (1), tBu (2), Ph (3)). For the first time, the crystal structure of a nickel(O) alkyne complex carrying phosphite ligands (2) has been determined. The reaction of (dipy)Ni(cod) (L2 = dipy) with butadiynes R'C ≡ C -C ≡ CR is strongly influenced by the substituents of the butadiyne. With R' = R = SiMe3 (4), tBu (5) and Ph (6) or R' = Ph, R = SiMe3 (7) and R ' = tBu, R = SiMe3 (8) mononuclear complexes (dipy)Ni(η2(1:2 )-R'C ≡ C-C ≡ CR ) have been observed. Depending on the stoichiometry with R = R' = Ph (9) and tBu (10) dinuclear complexes {(dipy)Ni}2(μ-η2(1:2),η2(3 :4 )-R'C ≡ C -C ≡ CR ) having two Ni atoms coordinated to two C ≡ C triple bonds were obtained. By contrast, with R' = R = SiMe3 (11), R' = tBu, R = SiMe3 (12) and R' = Ph, R = SiMe3 (13) the two Ni-centers were found to coordinate to the same C≡C triple bond to yield another type of a dinuclear complex {(dipy)Ni}2(μ-η2(1:2),η2(1:2 )-R'C ≡ C -C ≡C R). Compound 5 has been characterized by Xray crystal structure analysis. The structures of 2 and 5 are compared to that of the wellknown complex (Ph3P)2Ni(η2(1:2 )-tBuC ≡ C-C ≡CtBu) [1] to study the influence of different ligands L on the structural details. In comparison to the alkyne complexes L2Ni(η2-RC≡CR) in butadiyne complexes of the L2Ni(η2(1:2 )-R'C ≡ C-C ≡ CR ) type there is only a slight effect of the different ligands. The uncomplexed C ≡ C triple bond as a part of the second substituent in conjugation to the complexed C ≡ C triple bond appears to level out the influence of ligands and substituents.
Zum Substituenteneinfluß in neuen Ni(0)-Butadiin-Komplexen / On the Influence of Substituents in New Ni(0) Butadiyne Complexes
Authors: Rosenthal Uwe , Pulst Siegmar , Arndt Perdita , Baumann Wolfgang , Tillack Annegret , Kempe Rhett
Published: February 2015

It has been shown that disubstituted butadiynes react with (Ph3P)2Ni(C2H4) [1] or (cod)2Ni [2] in the presence of Ph3P to yield mononuclear complexes (Ph3P)2Ni(η2(1 :2 ) - R'C ≡ C - C ≡CR) (R' = R = SiMe3 (1), tBu (2) Ph (3) and R' = tBu, R = SiMe3 (4) or R' = Ph, R = SiMe3 (5)) or dinuclear complexes {(Ph3P)2Ni}2(μ-η2(1 :2),η2(3 :4) - R'C ≡C - C ≡CR ) (R' = R = SiMe3 (6), Ph (7)) depending on the stoichiometry applied. For R' = R = tBu or R' = tBu, R = SiMe3 the dinuclear complexes could not be obtained. Some of the mononuclear complexes with symmetrical (R' = R = SiMe3, tBu, Ph) and unsymmetrical disubstituted (R' = tBu, R = SiMe3) butadiynes have been characterized by X-ray crystal structure analysis to study the influence of different substituents on the structural details of the bonding. As compared to the alkyne complexes (Ph3P)2Ni(η2-RC ≡CR ) the influence of the different substituents in mononuclear butadiyne-complexes (Ph3P)2Ni(η2(1:2) - R'C ≡C - C ≡CR ) is strongly diminished by the conjugated uncomplexed C ≡C triple bond.
Synthesis, Characterization and Monoalkene Polymerization Activity of Bis-[(1,2,3,4-tetraphenyl)-η5-cyclopentadienyl]zirconium(IV) Dichloride
Authors: Conti Giuseppe , Arribas Guillermo , Altomare Angelina , Mendez Bernardo , Ciardelli Francesco
Published: February 2015

The title complex (1) has been prepared by reaction of ZrCl4 with 1,2,3,4-(tetraphenyl)- cyclopenta-1,3-dienyl lithium (2). The phenyl substituents on the metallocene ligands exert both steric and electronic effects on the active site obtained by activation of 1 with MAO. Thus this catalytic system shows lower polymerization activity than in case of unsubstituted or methyl-substituted ligands and leads to the formation of ethylene oligomers.
Palladium Catalyzed Alternating Cooligomerization of Ethylene and Carbon Monoxide to Unsaturated Ketones
Authors: Keim Wilhelm , Maas Heiko , Mecking Stefan
Published: February 2015

Cationic palladium catalysts have been used to cooligomerize ethylene and carbon monoxide. At high ethylene/CO ratios (m /m = 10:1) in methylene chloride as a solvent, unsaturated alternating cooligomers of the general structure R[C(O)CH2CH2]mH ( m ≥ 1 ; R ≡CH2=CH-, CH2=CHCH2CH2- and CH3CH = CHCH2-) were obtained for the first time. Single component catalyst precursors [(allyl)Pd(P^X )]+Y- (P^X = Ph2P(CH2)nC(= O )OR, Ph2P(CH2)2P(=O)Ph2, Ph2P(CH2)n

Ph2P(CH2)2S (=O )Ph, n = 1 - 3 , R = Me, Et; Y- = BF4
-, SbF6
- ) with bidentate P,O- and P,S-ligands as well as in situ catalysts with unfunctionalized phosphine ligands were used. With P"Bu3 as a ligand, selectivities for ethylvinylketone of 40% based on the CO converted were obtained. The hemilabile phosphino-ester and phosphinothiophene ligands behave like monodentate phosphines under catalytic conditions.
Ein tricyclisches Tetraboradisiladodecan aus Dimethyl-di-1-propinylsilan und Ethyldiboranen(6) / A Tricyclic Tetraboradisiladodecane from Dimethyl-di-1-propynylsilane and Ethyldiboranes(6)
Authors: Köster Roland , Seidel Günter , Boese Roland , Wrackmeyer Bernd
Published: February 2015

The exhaustive hydroboration of the (C ≡ C )-groups in Me2Si(C ≡ CMe)2 (A ) by adding ethyldiboranes(6) at room temperature is presumed to lead initially to the formation of a mixture of the threo- and erythro-3,3,5,6-tetrakis(diethylboryl)-4,4-dimethyl-4-silaheptanes (1a , b). The threo-1a reacts further by

borane catalysed intermolecular condensation to the substituted disilatetraboratricyclo[6.2.1.16.9]dodecane 2 with the formula

, whose crystal structure [space group C2/c, a = 19.696(2), b = 10.371(1), c = 16.580(2) Å; β = 125.90(1)°; at 122 K] has been established by X -ray diffraction. In contrast, the erythro-1b undergoes intramolecular, thermal elimination of Et3B to give the 1,2-diethyl-2,4-bis(diethylboryl)- 3,3,5-trim ethyl-3-silaborolane (4). If A is added to an excess of undiluted B (“hydridebath”), then the two substituted diastereomers of the 1-carba-arachno-pentaboranes(10)

(endo/exo-Et,SiH Me2) (3a, b), are formed preferentially as the result of an initial Si-C ≡-c le a v e d hydroboration.
A Rigid C1-Bridged Ansa-Zirconocene-Derived Catalyst System Suited for Stereoselective Low Molecular Weight Polypropylene Formation
Authors: Erker Gerhard , Psiorz Christian , Fröhlich Roland
Published: February 2015

2,5-Hexanedione was converted into the bisfulvene 2, then treated with two molar equivalents of methyllithium to yield the [4-cyclopentadienylidene-4,7,7-trimethyl-4,5,6,7-tetrahydroindenyl] dilithio compound 4. Hydrolysis, followed by treatment with acetone/pyrrolidine, gave the corresponding fulvene system 5. Reaction of 5 with methyllithium followed by treatment with ZrCl4 furnished the ring-annulated C1-bridged ansa-metallocene 8, bearing a tert-butyl substituent at the Cp ring, as a 1:1 mixture of two diastereoisomers. Treatment of the fulvene 5 with LiAlH4 followed by ZrCl4 yielded the respective isopropyl-substituted ansa-metallocene diastereomers 9a and 9b. Complex 9b was separated by fractional crystallization and characterized by X-ray diffraction. Complexes 8 and 9 provide active homogeneous Ziegler-type catalyst systems upon activation with excess methylalumoxane producing low molecular weight isotactic polypropylene with high catalyst activities.
Über das Erdalkalimetall-Lanthanoid-Kupfer-Oxomolybdat (Cu0,22Mg0 ,78)BaNd2Mo4O16/The Alkaline Earth Rare Earth Copper-Oxomolybdate (Cu0.22Mg0.78)BaNd2Mo4O16
Authors: Szillat H. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of (Cu0.22Mg0.78)BaNd2Mo4O16 have been prepared by crystallization from melts and investigated by X-ray methods. The compound crystallizes monoclinically, space group C6
2h - C12/c1, Z = 4, a = 5.351(1), b = 12.891(2), c = 19.391(4) Å,β = 90.899(14)° and is isotypic to CuKHo2Mo4O16. The crystal structure is dominated by BaO10 and NdO8 polyhedra forming a three-dimensional polyhedra network, which is filled by axially distorted (Cu,Mg)O6 octahedra and MoO4 tetrahedra.
Über einen 9L-Perowskit der Zusammensetzung Ba9Ru3,2Mn5,8O27/ On a 9L-Perovskite of the Composition Ba9Ru3.2Mn5.8O27
Authors: Frenzen S. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of Ba9Ru3.2Mn5.8O27 have been prepared by flux techniques. X-ray four circle diffractometer measurements led to trigonal (rhombohedral) symmetry, space group D5
3d - R3̄̄̄m , a = 5.7043(5), c = 21.255(4) Å , Z = 1. This phase is isotypic to BaRuO3. The crystal structure and the occupation of the M3O12 triple octahedra by ruthenium and manganese are discussed with respect to other oxides containing M3O12 groups in an ordered and disordered way.
Wechselwirkungen in Kristallen 62 [1, 2] Kristallisation und Strukturbestimmung von 2,5-Bis(trimethylsilyl)-p-benzochinon und von 2,5-Bis(trimethylsilyl)hydrochinon-natrium-bis(dimethoxyethan), einem Polymer-Strang mit Chelat-überkappten Wasserstoffbrücken (⊖O···HO)Na⊕(DME)2/ Interactions in Crystals, 62 [1, 2] Crystallization and Structure Determination of 2,5-Bis(trimethylsilyl)-p-benzoquinone and of 2,5-Bis(trimethylsilyl)hydroquinone Sodium Bis(dimethoxyethane), a Polymer String with Chelate-Capped Hydrogen Bridges (⊖O···HO)Na⊕(DME)2
Authors: Bock Hans , Nick Sabine , Näther Christian , Ruppert Klaus
Published: February 2015

From the electron and proton transfer equilibria network of quinones in solution a novel intermediate can be prepared by deprotonation of 2,5-bis(trimethylsilyl)hydroquinone to its monoanion using sodium metal. The sodium salt crystallizes in polymer strings connected via O⊖···(H)O hydrogen bridges, which are capped additionally by twofold dimethoxy-ethanesolvated Na⊕ countercations. The single crystal structure determination reveals one of the shortest O⊕ ··· HO distances observed so far of only 246 pm. MNDO calculations further confirm the assignment of hydroquinone monoanion building blocks in the polymer chain. For structural comparison as well as for attempts of its sodium reduction, 2,5-bis(trimethylsilyl)-p- benzoquinone has been synthesized. Its single crystal structure is reported, which does not show any cyanine distortion.
Darstellung, Schwingungsspektren und Normalkoordinationsanalyse der D- und 13C-Isotopomeren des Methylpentahydro-closo-hexaborats [B6H5(CH3)]2- sowie Kristallstruktur von [P(C6H5)4][B6H6(CH3)] / Preparation, Vibrational Spectra and Normal Coordinate Analysis of the D and 13C Isotopomeres of the Methylpentahydro-closo-hexaborate [B6H5(CH3)]2- and the Crystal Structure of [P(C6H5)4][B6H6(CH3)]
Authors: Baurmeister J. , Franken A. , Preetz W.
Published: February 2015

The crystal structure of [P(C6H5)4][B6H6(CH3)] has been determined by single crystal X-ray diffraction analysis; triclinic space group P 1̄ with a = 7.408(2), b = 11.887(3), c = 14.4486(9) Å , α = 80.013(12), β = 79.421(10), γ = 88.85(2)°. The additional H atom could be refined with B - H distances between 1.21 and 1.31 Å above one of the facettes of the B6 octahedron adjacent to the methyl group. The IR and Raman spectra of the ueprotonated Cs salts of the six isotopomers [B6H5(CH3)]2-, [B6H5(CD3)]2-, [B6H5(13CH3)]2-, [B6D5(CH3)]2-, [B6D5(CD3)]2- and [B6D5(13CH3)]2- exhibit characteristic shifts of their vibration bands. Using the crystallographic data a normal coordinate analysis has been performed, based on a general valence force field. With a set of 14 force constants (e.g. fd(BB ) = 1.80, fd(BC ) = 3.70, fd(BH ) = 3.17, fd(CH ) = 4.62 mdyn/Å) good agreement between observed and calculated frequencies o f all D and 13C isotopically labeled derivatives has been achieved. The potential energy distribution on the force constants reveals strong vibrational couplings of the boron cage with the substituents. The B - C stretching vibration o f the CH3 group is observed in the region 1142-1153 cm-1, for the CD3 substituent at higher frequencies of 1168-1179 cm-1.
Einstufige Synthese von Oxazolo[3′,2′ : 1,2]pyrido[3,4-b]indolen durch direkte Kondensationsreaktion von 3,4-Dihydro-β-carbolin mit α-Hydroxy-γ-butyrolactonen / One-Step Synthesis of Oxazolo[3′,2′ : 1,2]pyrido[3,4-b]indoles by Condensation of 3,4-Dihydro-β-carboline with α-Hydroxy-γ-butyrolactones
Authors: Weber Ulrich , Wanner Klaus Th.
Published: February 2015

A simple method for the synthesis of substituted oxazolo[3ʹ,2ʹ: 1,2]pyrido[3,4-b]indoles from 3,4-dihydro-β-carboline and α-hydroxy-γ-butyrolactones is described.
Zur Kristallchemie eines Silber-Cadmium-Oxovanadats: AgCdVO4 / On the Crystal Chemistry of a Silver Cadmium Oxovanadate: AgCdVO4
Authors: Münchau S. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of AgCdVO4 have been prepared in closed silver tubes using V2O5 as a flux. The light-orange crystals show orthorhombic symmetry, space group D16
2h-Pnma, a = 9.786(2), b = 6.994(1), c = 5.439(1) Å, Z = 4. The hitherto unknown AgCdVO4 is related to the Olivine structure but isotypic to Ag2CrO4 and NaCd4(VO4)3 respectively. The differences in crystal chemistry between the Olivine type, NaCd4(VO4)3 and AgCdVO4 are discussed.
Hochtemperatursynthese und Kristallchemie der Oxotantalate Cr2+
0,761Ta2,095O6 und FeTa2O6 / High Temperature Synthesis and Crystal Chemistry of the Oxotantalates Cr2+
0,761Ta2,095O6 and FeTa2O6
Authors: Peters E. , Müller-Buschbaum Hk.
Published: February 2015

Black single crystals of Cr0.761Ta2.095O6 have been prepared by CO2-LASER techniques. This phase crystallizes with monoclinic symmetry, space group C5
2h-P21/c, a = 4.748(1). b = 4.750(2), c = 10.405(3) Å, β = 117.152(13)°, Z = 2. The crystal structure is closely related to the trirutile type, although the metal positions are partly statistically occupied by Cr2+ and Ta5+ or underoccupied by Ta5+, respectively. FeTa2O6, prepared by the same m ethod does neither show any statistic occupation nor deviations from the trirutile structure, space group D14
4h-P42/mnm, a = 4.7595(5) Å, c = 9.201(2)A, Z = 2 .
K19Pb8O4(OH)3 und KPb: Ein Oxid-Hydroxid und eine Zintl-Phase mit [Pb4]4--Anionen / K 19Pb8O4(OH)3 and KPb: An Oxide-Hydroxide and a Zintl Phase with [Pb4]4- Anions
Authors: Röhr Caroline
Published: February 2015

K19Pb8O4(OH)3 crystallizes in the cubic system with space group Fm3m (a = 1622.7(4) pm: Z = 4). KPb crystallizes with the NaPb structure type (tetragonal, space group 141/acd, a = 1153.2(6) pm. c = 1886.8(9) pm. Z = 32). The crystal structures of both com­pounds contain Zintl-anions [Pb4]4- as characteristic building units, which in the Zintl phase are separated by potassium cations only. The oxide-hydroxide contains additional anions O2- and OH- enclosed by potassium ions in an octahedral coordination. The oxygen centered octahedra form a three-dimensional network of clusters [(O/OH)6K19] (consisting of six octahedra [(O/OH)K6] sharing edges) and single octahedra [OK6] connected by com­mon corners. Tlie [Pb4]4- tetrahedra occupy the voids within this framework.
Reaktionen von 2-Methyl-1H-benzimidazol mit Schwefelkohlenstoff und Phenylisothiocyanat. Kristall- und Molekülstruktur von 1,1′ -Carbonothioyl-bis(2-methyl-1H-benzimidazol) und 2-Methyl-1-(ethoxycarbonylmethylthio-phenylimino)-1H-benzimidazol / Reactions of 2-Methyl-1 H-benzimidazole with Carbon Disulfide and Phenyl Isothiocyanate. Molecular and Crystal Structures of 1,1′-Carbonothioyl-bis(2-methyl-1 H-benzimidazole) and 2-Methyl-1-(ethoxycarbonylmethylthio-phenylimino)-1 H-benzimidazole
Authors: Dölling Wolfgang , Hartungb Helmut , Biedermann Matthias
Published: February 2015

2-Methyl-1 H-benzimidazole 1 reacts in the presence of two equivalents of sodium hydride in dry DMSO with carbon disulfide to methyl 2-methylbenzimidazole-1-dithiocarboxylate 3 using methyl iodide as alkylating agent, whereas using 1,2-dibromoethane 1,1′-carbonothioyl bis(2-methyl-1 H-benzimidazole) 5 is formed. Compound 1 reacts with phenyl isothiocyanate in the presence of one equivalent of sodium hydride in dry DMF after alkylation to 2-methyl-1-( alkylthio-phenylimino)-1 H-benzimidazoles 6a, 6b. Reaction products 5 and 6b have been identified and structurally characterized by X-ray analysis.
Die Kristallstruktur von [SnCl4(Ph2PCH2-CH 2PPh2)]·CH2Cl2 / Crystal Structure of [SnCl4(Ph2PCH2-CH 2PPh2)] · CH2Cl2
Authors: Kunkel Frank , Dehnicke Kurt , Goesmann Helmut , Fenske Dieter
Published: February 2015

[SnCl4(Ph2PCH2-CH2PPh2)] CH2Cl2 has been characterized by a crystal structure determ ination. Space group P21/c, Z = 4, 5565 observed unique reflections with I > 2 σ(I), R = 0.043. Lattice dimensions at -70 °C: a = 1141.4(6), b = 2178.3(11), c = 1399.1(7) pm, β = 108.96(3)°. The complex forms monomeric molecules with the 1.2-bis(diphenylphosphino)ethane as chelating ligand. Bond lengths (average): Sn - P 266.7 pm, Sn - Cl 241.8 pm.
Ein Beitrag zur Synthese und Kristallchemie des Alkalimetall-Kupfer -Oxomolybdats Rb0,6K0,4CuMo3O10 / A Contribution on the Synthesis and Crystal Chemistry of the Alkaline Copper Oxomolybdate Rb0.6K0.4CuMo3O10
Authors: Szillat H. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of Rb0.6K0.4CuMo3O10 have been prepared by crystallization from melts and investigated by X-ray diffractometer technique. They crystallize with orthorhombic symmetry, space group D2h
16 -Pnma , a = 8.606(2), b = 7.595(3), c - 13.660(7) Å, Z = 4. The crystal structure of Rb0.6K0.4CuMo3O10 is characterized by the rare octahedral coordination of molybdenum and is related to (NH4)2Mo3O10 with respect to the one-dimensional 1
∞[Mo3O10]- chains.
Synthese und Molekülstrukturen der Molybdän(II)-Komplexe MoCl2(PMe3)2 und [Mo(μ-PPh2)(PPh2)(PMe3)]2 / Synthesis and Molecular Structures of the Molybdenum(II) Complexes MoCl2(PMe3)2 and [Mo(μ-PPh2)(PPh2)(PMe3)]2
Authors: Fromm Katharina , Plaikner Monika , Hey-Hawkins Evamarie
Published: February 2015

Li2P(2,4,6-Me3C6H2) reacts with Cp°MoCl2(PMe3)2 (Cp° = C5Me4Et) with reductive cleavage of the Mo -Cp° bond to yield MoCl2(PMe3)2 (1). The reaction of the Mo(II) derivative MoCl2(PMe3)4 with two equivalents of KPPh2(dioxane)2 yields [Mo(μ-PPh2)(PPh2)(PMe3)]2 (2). Both have been characterized by X-ray crystal structure determination.
Alkinol- und Alkindiol-substituierte Titanocen-Komplexe; Synthese, Reaktionsverhalten und Strukturmerkmale / Alkyne-ol and Alkyne-diol Substituted Titanocene Complexes; Synthesis, Reaction Behaviour and Structural Features
Authors: Lang Heinrich , Köhler Katrin , Herres Mathias , Emmerich Christiane
Published: February 2015

The reaction of (η5-C5H4SiMe3)2TiCl2 (1) with HO(CH2)nC ≡ CR (2a: n = 1, R = H; 2b: n = 1, R = CH3; 2c: n = 1, R = CH2OH ; 3: n = 2, R = H; 4: n = 4, R = H) affords in toluene at 25 °C in the presence of NEt3 the monoalkyne-ol substituted titanocenes (η5-C5H4SiMe3)2Ti(Cl)[O(CH2)nC ≡ CR] (5a: n = 1. R = H; 5b: n = 1, R = CH3; 5c: n = 1, R = C H2OH; 6: n = 2, R = H; 7: n = 4. R = H ).

Compound 5c reacts with one equivalent of 1 in the presence of NEt3 to yield (η5-C5H4SiMe3)2(Cl)Ti-OCH2C ≡ CCH2O -Ti(Cl)(η5-C5H4SiMe3)2 (8). In addition, compound 8 can be synthesized directly by treatment of (η5- C5H4SiMe3)2TiCl2 (1) with 0.5 equivalents of HOCH9C≡CCH2OH (2c) in the presence of NEt3. The reaction of (η5-C5H4SiMe3)2Ti(Cl)(OCH2C ≡ CCH3) (5b) with Co2(CO)8 (9) yields (η5-C5H4SiMe3)2Ti(Cl)[(η2-OCH2C ≡ CCH3)Co2(CO)6] (10). Treatment of 5b or 10 with HCl(aq) (11) leads to the formation of (η5-C5H4SiMe3)2TiCl2 (1) and HOCH2C ≡ CCH3 (2b) (reaction of 5b with 11) or (η5-C5H4SiMe3)2TiCl2 (1) and [(η2-HOCH2C ≡ CCH3)Co2(CO)6] (12) (reaction of 10 with 11).

All compounds have been characterized by analytical and spectroscopic data (IR , 1H, 13C NMR, MS) and (η5-C5H4SiMe3)2Ti(Cl)(OCH2C ≡ CCH3) (5b) by X -ray analysis.
Y7I12C2N: Eine Verbindung aus Einheiten zweier Y6(C2)-Oktaeder und eines Y6N2-Tetraederdoppels / Y7I12C2N: A Compound with Units of Two Y6(C2) Octahedra and a Y6N2 Double Tetrahedron
Authors: Mattausch Hansjürgen , Borrmann Horst , Eger Roland , Kremer Reinhard K. , Simon Arndt
Published: February 2015

The new compounds Y7I12C2N and Ho7I12C2N have been prepared by reaction of stoichiometric amounts of the metals (RE), REI3, REN and C in closed Ta capsules at 1150 and 1120K, respectively. Pure samples of the compounds were obtained after 5 days annealing time. The crystals with xenomorphic shape are olive-green (Y7I12C2N) or red-brown (Ho7I12C2N) in colour and sensitive to air and moisture. Y7I12C2N crystallizes in the space group P 1̄ (No. 2) with lattice constants a = 971.24(7), b = 1030.38(7), c = 1673.58(11) pm and α = 101.366(5), β = 92.758(5), γ = 112.799(5)°. According to Guinier photographs Ho7I12C2N is isotypic with the lattice consiants u - 968.8(3), b = 1028.7(3), r. = 1667.8(5) pm and α = 101.31(2), β = 92.78(2), γ = 112.80(1)°.

In the structure the C atoms are present as C2 units with a C -C distance of 144 pm. These C2 units are octahedrally coordinated by Y atoms (o1). The N atoms are in the center of Y4 tetrahedra, which are linked via a common edge to form double tetrahedra (t2). By condensation of N-centered double tetrahedra (t2) with a C2-centered Y octahedron (o1) the characteristic units o1t2o1 are formed. The I atoms coordinate all free edges and corners of these units and connect them via Ii - Ia contacts parallel [100] and [001].

The compounds are semiconducting. Ho7I12C2N exhibits Curie-Weiss behaviour with θ = 15(1) K and μeff = 10.5(1) μB.
O-Silylierte Phosphinoketenacetale RR′PCH2CH=C(OSiMe3)OR″. Darstellung und Hydrolyse zu Phosphinoestern / O -Silylated Phosphinoketenacetals RR′PCH2CH = C(O SiMe3)OR″. Preparation and Hydrolysis to Phosphinoesters
Authors: Wolfsberger Werner , Burkart Wolfgang , Werner Helmut
Published: February 2015

Trimethylsilyl phosphines Ph(R)PSiMe3 (R = Me, Et, Pr, Bu, iBu, and C5H11) react with acrylic esters CH2 = C(R′)CO2Me(R′ = H, Me) to give the O-silylated phosphinoketenacetals Ph(R)PCH2C(R′)=C(OSiMe3)OMe 1-6, 15 and 16. By contrast, the reactions of the sterically demanding silyl phosphines R2PSiMe3 (R = iPr, tBu) with CH2= CHCO2R′ (R′ = Me, Et) result in the formation of mixtures of the corresponding phosphinoketenacetals 7-10 and the 1,2-addition products R2PCH2CH(SiMe3)CO2R′ 11-14. The ratio of the two isomers depends on the solvent and on the reaction temperature. β-Substituted acrylic acid esters such as methyl trans-crotonate or methyl trans-cinnamate react only very slowly (yielding a mixture of compounds) or do not react at all. NMR spectra and NOE measurements reveal that only the Z-isomer of the O-silylated phosphinoketenacetals is formed. On the basis of these results a plausible reaction mechanism is proposed. The phosphinoketenacetals react with H2O to afford the phosphinoesters R(R′)PCH2CH2CO2R″ 17-22, and with D2O to give the deuterated species R(R′)PCH2CHDCO2Me 23 and 24.
Chloro-N,N-dialkylamino-2,2,2-trichloro-tert-butoxy-phosphines, New Reagents in the Syntheses of Oligonucleotides
Authors: Klein Manuela , Ugi Ivar
Published: February 2015

Chloro-N,N-dimethylamino- and chloro-N,N-diisopropylamino-2.2,2-trichloro-tert-butoxyphosphine are demonstrated as reagents in the automated solid-phase oligonucleotide syntheses.
Structure and Conformation of Photosynthetic Pigments and Related Compounds 9 On the Structure and Macrocycle Conformation of Two Copper(II) Rhodochlorin Derivatives and Two Related Rhodoporphyrins
Authors: Senge Mathias O. , Ruhlandt-Senge Karin , Lee Shwn-Ji H. , Smith Kevin M.
Published: February 2015

Crystal structure analyses of (rhodochlorinato-15-acetic trimethyl ester)copper(II) 3 and (31, 32-didehydro-rhodochlorinato-15-formic acid trimethyl ester)copper(II) 4 reveal intriguing multiple macrocycle conformations of the metallochlorins in the crystal. The observed conformations range from almost planar macrocycles to distorted macrocycles with individual atoms being displaced up to 0.72 Å from the mean plane. The nonplanar macrocycles show a S4-ruffled macrocycie distortion with significant distortions for the meso-carbons and tilting of the Cb- Cb axes. A comparison with the related free base porphyrins rhodoporphyrin-15- acetic acid trimethyl ester 5 and rhodoporphyrin dimethyl ester 6 shows that the conformational distortion is due to the mixing of metal and substituent effects, hydroporphyrin character, and packing forces. Crystal data: 3, monoclinic, P21, a = 12.096(4) Å, b - 14.307(4) Å, c = 22.343(9) Å , β = 104.94(4)°, Z = 4 (2 indep. mol.), R = 0.069 for 8141 reflections with I > 2.0σ(I); 4, triclinic, P 1, a = 10.528(3) Å . b - 10.646(4) Å, c = 34.026(13) Å, α = 89.81(4)°, β = 88.72(3)°, γ = 60.38(2)°, Z = 4 (4 indep. mol.). R = 0.073 for 9446 reflections with I > 2.5σ(I); 5, triclinic, P 1̄, a = 9.591(2) Å, b = 12.959(4) Å, c = 13.453(4) Å, α = 105.86(2)°, β = 92.67(2)°, γ = 96.12(2)°, Z = 2, R = 0.060 for 4990 reflections with I > 2.5 σ(I); 6, triclinic, P 1̄, a = 8.908(4) Å, b = 12.895(5) Å, c = 13.482(6) Å , α = 102.74(3)°, β = 90.38(4)°, γ = 91.84(3)°, Z = 2, R = 0.089 for 3369 reflections with I > 2.0σ(I).
Synthesis of a Chiral Meso-Like Ansa-Zirconocene Complex and its Use for the Catalytic Formation of Low Molecular Weight Polypropylene
Authors: Thiele Sven , Erker Gerhard , Fritze Cornelia , Psiorz Christian , Fröhlich Roland
Published: February 2015

Reaction of lithium(neomenthylcyclopentadienid) 3 with dimethyldichlorosilane gives dimethylbis[3-(neomenthyl)cyclopentadienyl]silane 4 regioselectively as a mixture of double bond shift isomers (57% isolated). Deprotonation with 2 equiv. of butyllithium followed by treatment with zirconiumtetrachloride furnished a mixture of the three {dimethylsilylenbis[η5-3-(neomenthyl)cyclopentadienyl][zirconium dichloride diastereomers from which the pure meso-like isomer 6e [p -R (1′S ,3 ′R ,4 ′R),p -S (1′S ,3 ′R ,4 ′R)] was isolated by fractional crystallization. Complex 6 c was characterized by an X-ray crystal structure analysis. Its D 1 - Zr - D 2 angle of 126.8° is very similar as observed in bis(η-cyclopentadienyl) zirconium dichloride (D 1 and D 2 denote the centroids of the cyclopentadienyl rings). The homogeneous 6c/methylalumoxane Ziegler-type catalyst produces polypropylene of low molecular weight (Mη ≈ 670 at ambient temperature). Related catalyst systems may find interesting applications in organic synthesis.
Oligophosphan-Liganden, XL. trans-Cyclopentan-1,2-diyl-bis(dicyclohexylphosphan) und trans-Norbornan-2,3-diyl-bis(dicyclohexylphosphan): Synthese und Enantiomerentrennung. Reaktionen von [trans-C5H8(PCy2 )2 ]PtH(CH2CMe3 ) mit C– H-Bindungen unter achiralen und chiralen Bedingungen / Oligophosphine Ligands, XL. trans-Cyclopentane-1 ,2-diyl-bis(dicyclohexylphosphine) and trans-Norbornane-2,3-diyl-bis(dicyclohexylphosphine): Synthesis and Separation of Enantiomers. Reactions of [trans-C5H8(PCy2)2]PtH (CH2CMe3) with C - H Bonds under Achiral and Chiral Conditions
Authors: Saare Andrea , Dahlenburg Lutz
Published: February 2015

The bis(dicyclohexylphosphines) trans-C5H8(PCy2)2 (1) and trans-C7H10(PCy2)2 (11) (C5H8 = cyclopentane-1,2-diyl, C7 H10 = norbornane-2,3-diyl) were prepared by treatment of the bis(dichlorophosphines) trans-C5H8(PCl2)2 and trans -C7H10(PCl2)2 with CyMgBr. Oxidation with H2O2 in acetone gave the corresponding P,P′-dioxides, trans- C5H8[P(O)C y2]2 (2) and trans-C7H10[P(O)Cy2]2 (12) respectively. Effective optical resolution of 2 was achieved using (2S,3S )-(+)-di-O-benzoyl tartaric acid as a resolving agent. Heating (+)-2 and (-)-2 in neat Ph2SiH2 gave enantiopure 1. Reactions of 1 and 11 with (cyclo-C8H12)Pt(CH2CMe3)2 afforded the dineopentyls [transC5H8(PCy2)2]Pt(CH2CMe3)2 , 3, and [trans-C7H 10(PCy2)2]Pt(CH2CMe3)2 (13). These were further derivatized to [trans- C5H8(PCy2)2]PtH (CH2CMe3) (5), and [trans-C7 H10(PCy2)2]PtH (CH2CMe3) (15) by consecutive acidolysis (HCl or (1S)-(+)-camphor-10-sulphonic acid) and treatment with Na[BH (OMe)3] of the acido(organo) intermediates [trans-C5H8(PCy2)2]PtCl(CH2CMe3) (4) and [trans-C7H10(PCy2)2]Pt[O3SCH2C9H13 (O ) -(+ ) ]CH2CMe3 (14) (mixture of four diastereoisomers), so obtained. Thermolysis of 5 in cyclo-C6H12/PhC2H, C6H6, or Me3SiOSiMe3 led to smooth formation of [trans -C5H8(PCy2)2]PtH (R ), R = C2Ph (6 ), C6H5 (8), CH2SiMe2OSiMe3 (9), and [trans -C5H8(PCy2)2]Pt(η2-PhC ≡CH ) (7), respectively. Reactions of enantiopure complex 5, prepared from (cyclo-C8H12)Pt(CH2CMe3)2 and resolved bis(phosphine) 1 via (+ )-/(-)-3 and (+)-/(-)-4, with 2,2′-dimethylbinaphthyl and 2 ,2′ -di-t-butylbiphenyl ( 2 equiv. in cyclo-C6H12 at 68 °C) resulted in little optical induction.
Supramoleküle aus Kronenethern und geminalen Sulfonen: Synthese von vier binären Komplexen und Kristallstruktur von (CH2CH2O)4·2H 2C(SO2C2H5)2/Supramolecules of Crown Ethers with Geminal Sulfones: Synthesis of Four Binary Complexes and Crystal Structure of (CH2CH2O )4·2H2C(SO2C2H5)2
Authors: Michalides Axel , Henschel Dagmar , Blaschette Armand , Jones Peter G.
Published: February 2015

In a systematic search for supramolecular complexes involving all combinations of the cyclic polyethers 12-crown-4 (12C4), 15-crown-5 (15C 5), 18-crown-6 (18C 6) and dibenzo- 18-crown-6 (DB -18C6), and the geminal di- or trisulfones H2C(SO 2Me)2, H2C (SO2Et)2 and HC (SO2Me)3-n (SO2Et)n (n = 0 -3 ) , only the following four complexes could be isolated and unequivocally characterized by elemental analysis and 1H NMR spectroscopy: [(12C4){H2C (SO2Et)2}2] (3), [(18C6){H2C (S O2Me)2}] (4), [(DB -18C 6){H2C (SO2Et)2}] (5) and [(D B -18C 6)2{HC (SO2Me )(SO2Et)2}3] (6). The structure of 3 (triclinic, space group P1̄) consists of crystallographically centrosymmetric formula units, in which the disulfone molecules are bonded on each side of the ring by two C -H ··· O(crown) interactions originating from the central methylene group (H···O 213 pm) and from the methylene group of one EtSO2 moiety ( H ··· O 237 pm). Formula units related by translation are connected into parallel strands by a third type of reciprocal C -H ···O bond (H ···O 232 pm) between the second H atom of the central methylene group and a sulfonyl oxygen atom of the adjacent unit. The structure of 4 (monoclinic, space group C2/c) showed severe disorder of the crown ether and could not be refined satisfactorily. Compounds 5 and 6 crystallized as long and extremely thin fibres, indicative of linear-polymeric supramolecular structures; single crystals for X-ray crystallography were not available.
Reindarstellung und Kristallstruktur von Lithiumtrinitridbromid, Li10N3Br / Preparation and Crystal Structure of Lithium Trinitride Bromide Li10N3Br
Authors: Marx Rupert
Published: February 2015

Li10N3Br has been prepared by the reaction of Li3N and dry, OH-free LiBr. It is found to be the most nitride rich compound in the quasi-binary system Li3-2xN1-xBrx. The previously unknown structure of the title compound has been solved from neutron powder diffraction data recorded using the flat-cone and powder diffractometer E2 at the Berlin BER II reactor. Li10N3Br crystallizes in the hexagonal space group P6̄m2 (No. 187), a = 741.3(1) pm, c = 386.57(3) pm, with one formula unit per unit cell. The structure is closely related to Li3N (space group P6/m m m , a = 364.8(1) pm, c = 387.5(1) pm). It comprises roughly pentagonal bipyramidal Li7N units which share edges and vertices to give a three-dimensional Li10N 3 network. The Li atoms in axial positions are in an almost linear coordination with the central N atom. The Li atoms in the equatorial positions are surrounded either by N atoms in an ideal trigonal coordination or by N and Br atoms in a distorted tetrahedral coordination. The Br atoms are situated in the large trigonal prismatic holes formed by the Li atoms.
Zur Synthese und Kristallstruktur von manganhaltigen Boratoxiden: MnFe(BO3)O und MnAl0,5Yo,5(BO3)O / Synthesis and Crystal Structure of Manganese Borate Oxides: MnFe(BO3)O and MnAl0,5Yo,5(BO3)O
Authors: Utzolino Anne , Bluhm Karsten
Published: February 2015

Single crystals of the compounds MnFe(BO3)O (I) and MnAl0.5Y0.5(BO3)O (II), were obtained by a B2O3 flux technique. I crystallizes with orthorhombic symmetry, space group D16
2h -Pnma (Nr.62), a = 939.92; b = 319.41; c = 939.11 pm; Z = 4 and II with monoclinic symmetry, space group C5
2h-P21/n (Nr. 14). a = 325.6; b = 955.1; c = 929.2 pm; β = 90.70° ; Z = 4. I is isotypic to the mineral Warwickite, while II is a distorded variant of this structure. All metal ions are octahedrally coordinated. Both structures contain isolated, trigonal planar BO3 units and oxygen atoms that are not coordinated to boron.
Zur Synthese und Kristallstruktur von Kupfercadmiumpyroboratoxid: Cu2Cd(B2O5)O / Synthesis and Crystal Structure of Copper Cadmium Pyroborate Oxide: Cu2Cd(B2O5)O
Authors: Münchau Sabine , Bluhm Karsten
Published: February 2015

Single crystals of the new compound Cu2Cd(B2O5)O have been prepared by B2O3/V2O5 flux technique in a closed silver tube. Their structure is isotypic with Cu2Co(B2O5)O but its preparation is quite different. X-ray investigations on single crystals led to the space group C5
2h-P21/c (Nr. 14), a = 339.9(2); b = 1509.8(2); c = 927,0(1) pm; β = 93.19(1)°; Z = 4. The structure contains isolated B2O5 groups and oxygen that is not coordinated to boron. Cadmium is octahedrally coordinated by oxygen, while copper exhibits a nearly square planar or a fivefold pyramidal coordination.
The Thorium Transition Metal Borides Th2TB10 (T = Fe, Co, Ni) with a Structure Very Similar to that of CaB6
Authors: Konrad Thomas , Jeitschko Wolfgang
Published: February 2015

The title compounds have been prepared by arc-melting cold-pressed pellets of the elemental components. They crystallize with a new structure type, which was determined from singlecrystal X-ray diffractometer data of Th2NiB10: Pbam, a = 564.6(2) pm, b = 1120.4(3) pm, c = 417.3(1) pm, Z = 2, R = 0.020 for 748 structure factors and 25 variable parameters. The structures of Th2FeB10 (a = 562.7(1) pm, b = 1126.1(3) pm, c = 418.3(2) pm) and Th2CoB10 (a = 562.4(1) pm, b = 1122.8(2) pm, c = 418.5(1) pm) were refined from single-crystal data to residuals of 0.025 (921 F values) and 0.032 (911 F values). The lattice of these ternary borides may be derived from that of ThB6 (Th2B12) with the cubic CaB6 type structure by replacing two of the linking boron atoms of adjacent B6 octahedra by a transition metal atom.
Crystal Growth, Room Temperature Crystal Structure and Phase Transitions of KMnPO4
Authors: Luján Marcos , Kubel Frank
Published: February 2015

Single crystals of KMnPO4 grown in a KCl flux show ferroelastic domains. The structure was determined on an optically controlled single domain crystal by X-ray diffraction methods. The cell is triclinic with dimensions a = 5.4813(5), b = 8.627(1), c = 8.887(1), in Å, α = 87.73(1)°, β = 89.10(1)°, γ = 88.01(1)°, Vᴍ = 419.6(1) Å3 and Z = 4. The structure is closely related to the stuffed β-tridymite type. DTA experiments between room temperature and 1000 °C and polarized light microscopy observations showed four phase transitions: at 165, 330, 353 and 707 °C.
[(TM EDA)2Li4Cl4(H2O)2]·2 TMEDA: stabförmige vierkernige Li-Komplexe verknüpft durch TMEDA / [(TM EDA)2Li4Cl4(H2O)2]·2 TMEDA: Stick-Like Tetranuclear Li Complexes Connected by TMEDA
Authors: Werner Bert , Neumüller Bernhard
Published: February 2015

The title compound 1 was synthesized by the reaction of LiCl with TM EDA (N,N,N′,N′- tetramethylethylendiamine) and water at 120 °C in boiling TM EDA. 1 was crystallized at - 30 °C as colorless crystals and characterized by NMR and IR spectroscopy as well as by an X-ray structure determination. 1 is a polymer in the solid state, built up by an alternating arrangement of stick-like tetranuclear Li complexes and two TMEDA molecules. The complexes and the TMEDA molecules are connected by hydrogen bridges in infinite chains.
Hindered Rotation in Poly(N-acyl)iminoalkylenes - A 13C Nuclear Magnetic Resonance Study
Authors: Rivas Bernabé L. , Albert Klaus , Geckeler Kurt E. , Bayer Ernst
Published: February 2015

Poly(N-acetyl)iminoethylene. poly(N-propionyl)iminoethylene and poly(N-acetyl)-2,2-dimethyliminoethylene were prepared by cationic polymerization in solution of 2-methyl- 2-oxazoline, 2-ethyl-2-oxazoline, and 2,4,4-trimethyl-2-oxazoline respectively. The 13C NMR spectra of the polymers obtained showed different sets of shifts for the carbon atoms of the backbone as well as for the N-acylimino side chain due to the restricted rotation of the Nacylimino group. The temperature dependence of the N-acylimino side chain signals showed a different coalescence behaviour depending on the substituents at both the main and the side chain.
Notizen: The Crystal Structure of Cesium Fluorotrioxochromate(VI), CsCrO3F
Authors: Rögner Peter , Range Klaus-Jürgen
Published: February 2015

The crystal structure of CsCrO3F was determined from single-crystal X-ray data as tetragonal, space group I41/amd, with a = 5.7429(3), c = 14.505(1) Å and Z = 4. The structure was refined to R - 0.028, Rw = 0.022 for 307 unique reflections.

In contrast to the earlier literature CsCrO3F is not isomorphous with scheelite but with α- CsReO4. The structure contains isolated CrO3F tetrahedra which are linked together by twelvefold coordinated Cs ions. The average Cr - O, F distance is 1.633(4) Å.
Untersuchungen an Polyhalogeniden, XIX [1] Bis(methyltriphenylphosphonium)oktaiodid (MePh3P)2I8, Cäsium(18-Krone-6)triiodid [Cs(C12H24O6)]I3, Iodoblei(18-Krone-6)triiodid [Pb(C12H24O6I]I3 und Diiodothallium(18-Krone-6)tetraiodothallat [Tl(C12H24O6)I2](TlI4) / Studies of Polyhalides, XIX [1] Bis(methyltriphenylphosphonium) Octaiodide (MePh3P)2I8, Cesium(18-crown-6) Triiodide [Cs(C12H24O6)]I3, Iodolead(18-crown-6) Triiodide [Pb(C12H24O6)I]I3 and Diiodothallium(18-crown-6) Tetraiodothallate [Tl(C12H24O6)I2](TlI4)
Authors: Tebbe Karl-Friedrich , El Essawi Mervat , El Khalik Sawsan Abd
Published: February 2015

(MePh3P)2l8 has been prepared by the reaction of methyltriphenylphosphonium iodide with iodine in ethanol. It crystallizes in the monoclinic space group P21/n with a = 985.2(2), b = 1260.0(1), c = 1872.6(4) pm, β = 91.50(2)° and Z = 4. The crystal structure has been refined to R = 0.030 for 2882 reflections. It may be described as a layerlike packing of cations and anions. The anion with point symmetry 1̅ consists of two triiodide groups and a bridging iodine molecule forming a rather common nearly planar Z-shaped octaiodide ion I8
2-.

[Cs(18-crown-6)]I3 has been prepared by the reaction of cesium iodide and 18-crown-6 with iodine in ethanol. It crystallizes in the triclinic space group P1̅ with a = 921.4(1), b = 1175.4(7), c = 1178.0(4) pm, a = 112.82(4), β = 94.24(7), γ = 98.60(3)° and Z = 2. The crystal structure has been refined to R = 0.038 for 3302 reflections. The geometry of the cation [Cs(18-crown-6)]+ and of the anion I3
- is quite normal.

[Pb(18-crown-6)I]I3 has been prepared by the reaction of lead iodide and 18-crown-6 with iodine in dichloromethane. It crystallizes in the monoclinic space group P 21/n with a = 833.6(3), b = 1721.0(6), c = 1730.6(6) pm, β = 99.61(3)° and Z = 4. The crystal structure has been refined to R = 0.047 for 2772 reflections. It consists of complex cations [Pb(18-crown-6)I]+ and triiodide anions I3- forming weakly bonded ion pairs.

[Tl(18-crown-6)I2](TlI4) has been prepared by the reaction of thallium(I)iodide and 18-crown-6 with iodine in dichloromethane. It crystallizes in the monoclinic space group P21/n with a = 1236.8(3), b = 1382.6(3), c = 1710.2(2) pm, β = 90.76(1)° and Z = 4. The crystal structure has been refined to R = 0.044 for 2916 reflections. It is composed of complex cations [Tl(18-crown-6)I2] + nd complex anions TlI4
- with their usual and expected geometry.
Offene und geschlossene Triferriophosphonium-Salze und Triferriophosphane / Open and Closed Triferriophosphonium Salts and Triferriophosphines
Authors: Pohl Wolfgang , Lorenz Ingo-Peter , Nöth Heinrich , Schmidt Martin
Published: February 2015

The reaction of P(SiMe3)3 with an excess of CpFe(CO)2X (X = Cl, Br) through the action of water gives the triferriophosphonium salt [{CpFe(CO)2}3PH]2FeX4 together with ferrocene as by-product. The cation of the salt can be deprotonated by DBU to afford the unstable triferriophosphine {CpFe(CO)2}3P. Its subsequent realkylation with RX ( R = Me, CH2Ph; X = I, Br) leads to alkyltriferriophosphonium salts [{CpFe(CO)2}3PR]X. Photolysis of [{CpFe(CO)2}3PH]2FeX4 induces the elimination of one CO group, and the CO-bridged and partly closed complex [{μ-CO(CpFeCO)2}{CpFe(CO)2}PH]2FeX4 is formed, the cation of which can also be deprotonated to give the corresponding monobridged phosphine (μ-CO(CpFeCO)2}{CpFe(CO)2}P. Both PH-phosphonium salts undergo a hydrogen-chlorine exchange reaction to give the P-Cl analogues [{CpFe(CO)2}3PCl]2FeX4 and [{μ-CO(CpFeCO)2}{CpFe(CO)2}PCl]2FeX4. The IR and NM R spectra of all species as well as the X-ray structure analyses of the open and closed P-H functional complexes are reported and discussed.
Zur Redoxchemie und Struktur von Oxovanadium(IV,V)-KompIexen mit substituierten Dibenzotetraaza[14]annulen Liganden / Redox Chemistry and Structure of Oxovanadium(IV.V) Complexes Containing Substituted Dibenzotetraaza[14]annulene Ligands
Authors: Schumann Hans
Published: February 2015

The oxovanadium(IV) complexes LVO and L′VO (L = dianion of 5,14-dihydro-6,8,15.17- tetramethyldibenzo[b.i][1,4.8,11]tetraazacyclotetradecine. H2L, and L′ = dianion of 5,14-dihydro-6,15-dimethyl-8,17-diphenyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecine, H2L′) are redox active as indicated by cyclovoltammetric measurements and confirmed by preparative methods: Reversible oxidation to the corresponding oxovanadium (V) cations is observed at ca. 0.35 V vs. SCE in CH2Cl2, and these cations are prepared in high yield by oxidation of the oxovanadium(IV) precursors with [(C5H5)2Fe]SbF6 (reversible by addition of cobaltocene). Irreversible reduction waves are observed for both complexes in the range -1 .9 to 2.1 V vs. SCE in CH2Cl2. Preparative reduction of LVO with Na/K alloy affords very unstable anionic oxovanadium(IV) complexes containing a deprotonated or reduced ligand, while with Li[B(C2H5)3H] in THF the Lewis acid/Lewis base adduct LVOxB(C2H3)3 is isolated. Spectroscopic data including ESR [vanadium(IV)] and 51V NMR [vanadium(V)] are given and discussed. The complexes LVO and [LVO]SbF6 have been characterized by single crystal Xray structure determinations.
Darstellung und spektroskopische Charakterisierung von Sn2PO4Br / Preparation and Spectroscopic Characterization of Sn2PO4Br
Authors: Narda G. E. , Pedregosa J. C. , Baran E. J. , Apella M. C.
Published: February 2015

The synthesis of a new Sn(II) phosphate halogenide, Sn2PO4Br, is described. The com pound was characterized by means of infrared and Raman spectroscopies as well as by its 119Sn-Mößbauer spectrum. The results are compared with those of other Sn2PQ4X species.
Octacidomycine, III: Synthetische Strukturanaloga aus C5-Bausteinen / Octacidomycins, III: Synthetic Structural Analogues from C5-Units
Authors: Krause Andreas , Lackner Helmut
Published: February 2015

The total synthesis of an isoprenoid-like analogue (2) of octacidomycin (1). a novel oligocarboxylic acid antibiotic, is described. Starting from 3 (Scheme 1) and the tetraethylester of 1,11-dibromoundecane-4,4,8,8,-tetracarboxylic acid (6) as a key compound systematical fragment condensations lead to the pentadeccicarboxylic acid 12 and hence to the 1,3,7,11,15,19,23,27-heptacosane-octacarboxylic acid 2. This contains regularly connected C5- instead of C7-units and shows contracted distances between the acid groups. The newly developed synthesis yields a hitherto unknown type of oligocarboxylic acids and some useful intermediates with one or two terminal vinylic functions (13-15 ).
N,N-Disubstituierte Nʹ-Ferrocenoylthioharnstoffe als zweizähnige Komplexliganden für Übergangsmetallionen. Kristallstruktur von Bis-(N,N-diethyl-Nʹ-ferrocenoylthioureato)nickel(II) / N,N-Disubstituted Nʹ-Ferrocenoyl Thioureas as Bidentate Ligands for Transition Metal Ions. Crystal Structure of Bis-(N,N-diethyl-Nʹ-ferrocenoylthioureato)nickel(II)
Authors: Seidelmann Oliver , Beyer Lothar , Richter Rainer
Published: February 2015

N,N-diethyl-Nʹ-ferrocenoyl-thiourea and N-(morpholino-thiocarbonyl)ferrocenecarboxylic amide have been prepared by the reaction of ferrocenoyl chloride with potassium thiocyanate and the respective amine in dry acetone. These bidentate ligands yield neutral heterometalIic complexes with Ni(II), Cu(II), Mn(II) and Co(III). The dark brown air stable crystals of bis-(N,N-diethyl-Nʹ-ferrocenoylthioureato)nickel(II) were characterized by X-ray structure de­termination. Lattice dimensions: a = 1870.9(1), 6= 1161.5(1), c = 1491.4(1) pm; space group Pca21, Z = 4, R = 0.030 for 5707 observed reflections.
UbergangsmetalIkomplexe mit Schwefelliganden, CXV+. Protonierung und Alkylierung der Thiolatdonoren von Ru(II)-Komplexen mit [Ru(′buS5′)]-Fragmenten (′buS5–H2 = 2,2′-Bis(2-mercapto-3,5-di-t-butylphenylthio)diethylsu!fid)/Transition Metal Complexes with Sulfur Ligands, CXV+. Protonation and Alkylation of Thiolate Donors in Ru(II) Complexes with [Ru(′buS5′)] Fragments (′buS5′–H2 = 2,2′-Bis(2-mercapto-3,5-di-t-butylphenylthio)diethylsulfide)
Authors: Sellmann Dieter , Rohm Christine , Moll Matthias
Published: February 2015

Reaction of meso-[Ru(L)(′buS5′)] complexes (L = CO (1), PPh3, PCy3) with one equivalent of oxonium salts R3OBF4 (R = CH3, C2H5) yields the C1 symmetrical monoalkyl derivatives [Ru(L)(′buS5′-R)]BF4 (L = CO, R = CH3 (2), C2H5 (3); L = PPh3, R = CH3 (5); L = PCy3, R = CH3 (6)), in which one of the thiolate donors of the starting complexes is alkylated diastereospecifically. Monoalkylation of the binuclear complex [Ru(′buS5′)]2 leads to C1 symmetrical [Ru(′buS5′-CH3)]2(BF4)2 (7) which gives the hydrazine complex [μ-N2H4{Ru(′buS5′-CH3)}2](BF4)2·N2H4 (9) upon reaction with N2H4.

Reaction of 1 with 1.5 equivalents of CF3SO3H yields the isolable thiol complex [Ru(CO)(′buS5′-H)]CF3SO3·0.5 CF3SO3H (4). The 1H-NMR spectra are temperature-dependent and indicate exchange of the thiol proton between the thiolate donors of the ′buS5′2- ligand. Twofold protonation of 1 could only be proved IR-spectroscopically, dialkylation of 1, however, yields isolable [Ru(CO)(′buS5′-(CH3)2)](BF4)2 (8) as a mixture of diastereomers.

The IR stretching frequencies ν(CO) of the CO complexes indicate that the electron densities at the ruthenium centers are decreased and the Ru-L bonds are weakened. However, the ligands L in the [Ru(L)(′buS5′-R)]BF4 complexes do not exchange more readily than in the parent complexes.
(Cyclopentadienyl)dihalogenochromium-Donor Compounds. Synthesis and NMR Investigation
Authors: Bräunlein Brigitte , Köhler Frank H. , Strauß Werner , Zeh Harald
Published: February 2015

A series of paramagnetic (S = 3/2) chromium half-sandwiches of the type CpCrX2D (D = donor) were synthesized by starting from [CpCrX2]2, Cp2Cr, CpCrCl2(THF), and Cp*Cr(CH3)2[P(CH3)3]. Besides the parent cyclopentadienyl (Cp) the alkylated derivatives CH3C5H4, (CH3)5C5 (Cp*), and C2H5(CH3)4C5 were bound to chromium. The electronegative substituent was X = F, Cl, Br, I, and triflate, while the donors were three ethers, four ketones, dimethylsulfoxide, acetonitrile, methylisocyanide, pyridine, and seven molecules ER3 where E = N, P, As, Sb. The half-sandwiches were partly isolated and partly established in solution. The 13C and 1H NMR spectra showed strongly shifted signals which allowed to quantitatively investigate the equilibrium between CpCrX2D and the anti ferromagnetic species [CpCrX2]2. The NMR signals of CpCrX2D and its substituted derivatives appeared in characteristic ranges thus providing a means of rapid identification. Considerable spin density was found to be induced on the ligands; it is negative in the Cp π system. As for the donors, inter- and intramolecular dynamic behavior as well as selective spin transfer to the γ protons of acetonitrile, methylisocyanide, and ketones was detected.