Published by De Gruyter

Volume 47 Issue 11

Issue of Zeitschrift für Naturforschung B

Contents
Journal Overview

Open Access June 2, 2014

Addition von O- und C-Nucleophilen an Ruthenium-Schwefeldioxid-Komplexe, Struktur von [cpRu(dppm)(SO₂Et)] / Addition of O- and C-Nucleophiles to Ruthenium Sulfur Dioxide Complexes, Structure of [cpRu(dppm)(SO₂Et)]

Wolfdieter A. Schenk, Peter Urban, Thomas Stährfeldt, Eberhard Dombrowski

Page range: 1493-1500

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Abstract

Ruthenium-sulfur dioxide complexes [cpRu(PR 3 ) 2 (SO 2 )]Cl ((PR 3 ) 2 = (PPh 3 ) 2 , Ph 2 PCH 2 PPh 2 (dppm), Ph 2 PC 2 H 4 PPh 2 (dppe)) add alkoxide to give sulfito complexes [cpRu(PR 3 ) 2 (SO 2 OR′)] (R′ = Me, Et, /Pr). Reactions of [cpRu(dppm)(SO 2 )]Cl with LiR′ (R′ = Me, Bu, Ph), MgBrR′ (R′ = Et, CH=CH 2 ) or ZnEt 2 give sulfinato complexes [cpRu(dppm)(SO 2 R′)]. The structure of [cpRu(dppm)(SO 2 Et)] was determined by X-ray crystallography: Crystals are triclinic, space group P1̄, a = 11,008(1), b = 15,998(6), c = 17,813(2) Å, α = 92,30(2), β = 93,916(8), γ = 107,54(2)°, Z = 4. Salient features are a short Ru-S bond and relatively long S-O bonds which attest to the high π-donor ability of the pseudo-tetrahedral metal fragment.

Open Access June 2, 2014

3,5-Diphenyl-1,2-dithiolium-hydrogensulfat – Bildung und Struktur / 3,5-Diphenyl-1,2-dithiolium Hydrogensulphate – Synthesis and Structure

Erhard Uhlemann,, Frank Weller

Page range: 1501-1504

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Abstract

3,5-Diphenyl-1,2-dithiolium hydrogensulphate was prepared by the reaction of bis(thiodibenzoylmethanato)-nickel(II) with thionyl chloride in acetonitrile solution. The compound was characterized by X-ray structure determination (1261 observed, independent reflexions, R = 0,056). Crystal data: a = 543,1(1), b = 1605,7(1), c = 1678,9(2) pm; space group P 2 1 2 1 2 1 , Z = 4. By hydrogen bonding the hydrogensulphate ions form chains of weakly helical structure.

Open Access June 2, 2014

Die Kristallstrukturen der Palladium(II)-Komplexe [Pd(CH₃CN)₄](BF₄)₂, [PdCl(μ₂ -PPh₂)(HPPh₂)]₂ · CH₂Cl₂ und [PdCl(HPPh₂) {H(OPPh₂)₂}] / The Crystal Structures of the Palladium(II) Complexes [Pd(CH₃CN)₄](BF₄)₂, [PdCl(μ₂-PPh₂)(HPPh₂)] · CH₂Cl₂, and [PdCl(HPPh₂){H(OPPh₂)₂}]

Thorsten Gebauer, Gerlinde Frenzen, Kurt Dehnicke

Page range: 1505-1520

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Abstract

The crystal structures of the title compounds were solved by X-ray methods. [Pd(CH 3 CN)4](BF 4 ) 2 : Space group Pbca, Z = 4,812 observed unique reflections, R = 0.057, wR = 0.033. Lattice dimensions at -80 °C: α = 1027.5(5), b = 1242.8(6), c = 1280.3(6) pm. The compound consists of planar [Pd(CH 3 CN)4] 2+ ions with Pd-N bond lengths of 195.6 pm and BF 4 - anions. [PdCl(μ 2 -PPh 2 (HPPh 2 )] 2 • CH 2 Cl 2 crystallizes in two polymorphic forms in the same space group type but with different cell parameters, which depends on the conditions of the synthesis. α-form: Space group P2 1 /c, Z = 4, 4680 observed unique reflections, R = 0.041, wR = 0.033. Lattice dimensions at -80 °C: a = 937.2(2), b = 1750.3(6), c = 1593.9(5) pm, β = 106.32(2)°. β-form: Space group Ρ2 1 /n, Ζ = 4, 2519 observed unique reflections, R = 0.105, wR = 0.067. Lattice dimensions at -80 °C: a = 1118.0(4), b = 1222.4(3), c = 1849.9(4) pm, β = 90.72(2)°. Both polymorphs contain centrosymmetric molecules [PdCl μ 2 - PPh 2 )(HPPh 2 )] 2 with Pd-P bond lengths of 226.6 pm for the bridging PPh 2 groups and Pd-P bond lengths of 232.2 pm for the terminal HPPh 2 ligands. [PdCl(HPPh 2 ){H(OPPh 2 ) 2 }]: Space group Pbca, Z = 8,3673 observed unique reflections, R = 0.038, wR = 0.032. Lattice dimensions at -80 °C: a = 1736.6(3), b = 1874.4(4), c = 1983.1(4) pm. The palladium atom has planar coordination consisting of the chlorine atom, the phosphorus atom of the HPPh 2 ligand (Pd-P bond length 235.5 pm), and by the two phosphorus atoms of the H(OPPh 2 ) 2 chelate (Pd-P bond lengths 225.9 and 231.0 pm).

Open Access June 2, 2014

Preparation and Crystal Structures of Th₅Fe₁₉P₁₂ and ThFe₄P₂

Jörg H. Albering, Wolfgang Jeitschko

Page range: 1521-1528

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Abstract

The new compounds Th 5 Fe 19 P 12 and ThFe 4 P 2 were prepared by reaction of the elemental components in a tin flux and their crystal structures were determined from single-crystal X-ray data. Th 5 Fe 19 P 12 crystallizes with a new monoclinic structure type: C2/m, a = 2920.3(3), b = 379.18(3), c = 931.48(8) pm, β = 103.36(1)°, Z = 2, R = 0.031. ThFe 4 P 2 is isotypic with SmNi 4 P 2 : P nnm, a = 1448.9(2), b = 1074.7(2), c = 376.98(4) pm, Z = 6, R = 0.030. Both compounds belong to the large family of structures with a metal : nonmetal ratio of exactly or nearly 2:1. In these phosphides all phosphorus atoms have nine metal neighbors: six are forming a trigonal prism with three additional neighbors capping the rectangular faces of the prism. In both structures the thorium atoms have trigonal prismatic or octahedral phosphorus coordination. Most iron atoms have the usual tetrahedral phosphorus environment. In addition, the structure of Th 5 Fe 19 P 12 has iron atoms in rectangular and distorted square pyramidal phosphorus coordination, while the structure of ThFe 4 P 2 contains iron atoms with only two or three phosphorus neighbors.

Open Access June 2, 2014

Synthese von Phosphaalkenclustern durch reduktive Phosphinidenfragmentierung zweizähniger Halogenphosphane RXP— CH₂ — PXR mit Fe₂(CO)₉ / Synthesis of Phosphaalkene Clusters by Reductive Phosphinidene Fragmentation of Bidentate Halogenphosphines RXP—CH₂—PXR with Fe₂(CO)₉

Frank Bitterer, David J. Brauer, Frank Dörrenbach, Jörg Fischer, Othmar Stelzer

Page range: 1529-1540

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Abstract

Reaction of halogen functional methylenebisphosphines 1 XRP–CH 2 –PRX (X = Cl, Br) with excess Fe 2 (CO) 9 affords μ 3 -phosphinidene clusters (5) containing phosphaalkene ligands R–P=CH 2 . The fragmentation of the P–C–P skeletons in 1 proceeds stepwise, phosphide complexes 2 and novel Fe 3 clusters 3 with RP–CH 2 –PR bridging units being formed as intermediates of the oxidative addition reductive elimination process. The X-ray structural analysis for 5b (R = NEt 2 ) reveals an Fe 3 (CO) 9 PR butterfly core to which the phosphaalkene ligand R–P=CH 2 (P=C bond length 1.766(4) A) is coordinated in a μ 3 ,η 2 -manner. In case of methylenebisphosphines 1 with bulky substituents (R = 2,4,6-iPr 3 C 6 H 2 ) the phosphinidene fragmentation of the P–C–P skeleton is accompanied by the formation of 2,3-dihydrobenzo[b]-phosphole ligands.

Open Access June 2, 2014

Photochemistry in Porous Materials, II / Photolysis of Benzoin Ethers in Silicalite

Gourkrishna Dasmohapatra, Thomas Wolff, Günther von Bünau

Page range: 1541-1544

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Abstract

Four benzoin ethers 1 (a: methyl-, b: ethyl-, c: isopropyl-, d: phenylether) were photolyzed inside the channel system of silicalite S- 115, a novel type of zeolite. Products which could be separated from the zeolite framework in various relative yields were pinacol ethers (from a, b, c), benzil (a–d), benzaldehyde (a–d), benzoates (a–d), and phenol (d). While the former three types of products clearly arise from Norrish type I cleavage of the parent molecules, a mechanism involving the enolic form of the benzoin ethers is proposed in order to explain the formation of benzoates and phenol.

Open Access June 2, 2014

Übergangsmetallkomplexe mit Schwefelliganden, XCII. Oxidation von Thiolat-Amin- zu Schiffbase-Eisen(II)-Komplexen. Röntgenstrukturanalyse und Reaktivität von [Fe('N₂S₂')]₂ (′N₂S₂′^2- = Glyoxal-bis(2-mercaptoanil)(2 – )) / Transition Metal Complexes with Sulfur Ligands, XCII. Oxidation of Thiolate Amine to Schiff Base Iron(II) Complexes. X-Ray Structure Analysis and Reactivity of [Fe(′N₂S₂')]2 (′N₂S₂′²- = Glyoxal-bis(2-mercaptoanil)(2–))

Dieter Sellmann, Marcus Hannakam, Falk Knoch, Matthias Moll

Page range: 1545-1550

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Abstract

Oxidation of [Fe(CO) 2 (′N 2 H 2 S 2 ′')] (1) (′N 2 H 2 S 2 ' 2 - = 1,2-ethanediamine-N,N′-bis(2-benzenethiolate)(2—)) gave insoluble [Fe(′N 2 S 2 ')] 2 (2) ('N 2 S 2 ' 2 - = glyoxal-bis(2-mercaptoanil)(2—)). Dinuclear, thiolato-bridged 2 was characterized by single crystal X-ray structure analysis. It does not react with CO or H 2 , but yields bis or mono adducts with PR 3 (R = Me, n-Bu, Cy).

Open Access June 2, 2014

Gasphasen-Reaktionen, 91 [1-3]<br />Thermische und heterogen-katalysierte N₂-Abspaltung aus Azo-Verbindungen R–N=N–R (R = CH₃, C₃H₅, C₆H₅) / Gas Phase Reactions, 91 [1-3]<br />Thermal and Heterogeneously Catalyzed N₂ Elimination of Azo-Compounds R–N=N–R (R = CH₃, C₃H₅, C₆H₅)

Hans Bock, Bodo Berkner

Page range: 1551-1560

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Abstract

Thermal decompositions of azo compounds in the gas phase under reduced pressure are further investigated using photoelectron spectroscopic gas analysis. Passing diallyl, diphenyl and phenylmethyl derivatives either through a short-pathway pyrolysis (SPP) apparatus or through an external thermal reactor (ETR) results in the following fragmentations: Under nearly unimolecular conditions (SPP, 10 -4 mbar pressure), diallyldiazene decomposes above 600 K to N 2 and hexadiene-1,5 with the allyl radical as a detectable intermediate. The PE spectra recorded for diphenyldiazene above 1000 K (ETR, 1 -2 mbar pressure) show N 2 , benzene, as well as traces of diphenyl. Phenylmethyldiazene yields above 800 K (SPP) predominantly N 2 , toluene, diphenyl and ethane with the methyl radical as the only detectable intermediate. Insertion of quartz wool into the pyrolysis tube (ETR) lowers the fragmentation temperatures, and in addition, above 850 K, HCN and aniline are PE spectroscopically identified. Surprisingly, this second reaction channel can be heterogeneously catalyzed: phenylmethyldiazene decomposes under 10 -2 mbar pressure at a [Ni/SiO2] catalyst surface selectively to HCN and aniline.

Open Access June 2, 2014

Unendliche Y₂(H₂O)₁₀[C₆(COO)₆]-Ketten in Y₂[C6(COO)₆] · 14H₂O / Infinite Chains of Y₂(H₂O)₁₀[C₆(COO)₆] in Y₂[C₆(COO)₆] · 14 H₂O

Christian Robl, Stephanie Hentschel

Page range: 1561-1564

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Abstract

Colourless monoclinic single crystals of Y 2 [C 6 (COO) 6 ]· 14H 2 O were grown in aqueous silica gel (space group P2 1 /n, a = 847.5(1), b = 923.4(2), c = 1632.0(3) pm, β = 100.33(1)°, Ζ = 2, 223 parameters, 1784 reflections, R g = 0.0357). Y 3+ is coordinated by 5 water molecules and 3 oxygen atoms of the mellitate anion in a dodecahedral fashion. Y 3+ and [C 6 (COO) 6 ] 6- ions are linked by coordinative bonds, yielding infinite chains of composition Y 2 (H 2 O) 10 [C 6 (COO) 6 ] extending parallel to [100]. Hydrogen bonds connect adjacent chains.

Open Access June 2, 2014

Crystal and Molecular Structure and Properties of Tetrasodium<br />[Bis { (µ-isothiocyanato-N,S)(N-salicylidene-β-alaninato) } dicuprate(II)] Dithiocyanate Tetrahydrate

V. Kettmann, J. Krätsmár-Šmogrovič, O. Švajlenová, M. Žemlička

Page range: 1565-1570

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Abstract

The binuclear antiferromagnetically superexchange-coupled aquabis(N-salicylidene-β-alaninato)dicopper(II) monohydrate reacts with NaSCN to yield a complex cuprate(II) of stoichiometry Na 2 Cu(sal-β-ala)(NCS) 2 · 2 H 2 O. The compound has a magnetic moment μ/eff = 1.85. μ Β (Τ = 295 K), and an axial EPR spectrum with g11 > g ⊥ . The crystal and molecular structure of the title compound has been determined and refined to R = 0.055 (Rw = 0.062) for 1535 observed reflections, [I > 2σ(I)]. The crystals are triclinic, space group P1̅, with cell dimensions: a = 6.989(3), b = 10.445(5), c = 12.692(6)Å; α = 84.88(5), β = 70.13(4), and γ = 86.72(6)°, V = 869 Å 3 ; Z = 2. The coordination environment of the Cu(II) atom is axially distorted square pyramidal (4 + 1). The basal plane of the pyramid is formed by the 01, Ν 1, and O 2 donor atoms of the tridentate sal-β-ala(2—) Schiff base ligand and by the N 2 atom of the additional NCS(1—) ligand. The apex of the pyramid is occupied by the weakly contacting S l′ atom of the bridging —NCS— ligand, Cu—S 1′ = 2.933(2) Å, thereby giving rise to [Cu 2 (sal-β-ala) 2 (μ-NCS)2] 2- centrosymmetric binuclear complex anion. The remaining components of the crystal structure are SCN- (uncoordinated to Cu 2+ ), Na+ ions, and H 2 O molecules.

Open Access June 2, 2014

Nitrosolate und verwandte Verbindungen, XII Nitrosolatokomplexe von Silber(I) / Nitrosolates and Related Compounds, XII Nitrosolato Complexes of Silver(I)

Falk Olbrich, Bärbel Zimmer, Michael Kastner, Carl von Schlabrendorff, Gottlieb Vetter, Günter Klar

Page range: 1571-1579

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Abstract

X-ray analysis shows silver(I) aminomethylnitrosolate to have dimers as structural units, in which the W-shaped nitrosolate ions act as μ 2 -bridging ligands via the nitrogen atoms of the NO groups. The nearly planar dinuclear complexes form stacks, which are connected by additional AgO contacts leading to a kind of layer structure. These layers are held together by hydrogen bonds. Mononuclear complexes of composition [Ag(nitrosolate)L 2 ] can be obtained from silver(I) ethylnitrosolate and bipyridyl in methanol and from silver(I) benzylnitrosolate and triphenylphosphane in diethylether/liquid ammonia. In these complexes the nitrosolate ions are supposed to act as chelating ligands, again with N,N′-coordination.

Open Access June 2, 2014

[Mn(SPh)₃Cl]²-, [Mn(SPh)₃Br]^2-, [Mn(SePh)₄]^2-, [Mn(TePh)₄]^2-, and [Co₄(SPh)₆Cl₄]^2-: New Mixed Halide/Thiolate and Chalcogenolate Complexes of Manganese and Cobalt

Wolfgang Tremel, Bernt Krebs, Klaus Greiwe, Wolfgang Simon, Hans-Oscar Stephan, Gerald Henkel

Page range: 1580-1592

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Abstract

The reactions of 1:1:1 molar ratio mixtures of NaSPh/MnCl 2 /Et 4 NBr and NaSPh/CoCl 2 / Et 4 NCl in methanol afford the compounds [Et 4 N] 4 [Mn(SPh) 3 Br][Mn(SPh) 3 Cl] (1) and [Et 4 N] 2 [Co 4 (SPh) 6 Cl 4 ] · MeCN (2), respectively, with the following crystal data: a = 14.408(5), b = 13.788(4), c = 17.984(5) Å, β = 90.16(2)°, space group P2 1 /c and Ζ = 4 for 1, and a = 21.976(4), b = 13.081(2), c = 22.012(4) Å, β = 105.48(1)°, space group P 2 1 /c for 2. The structures were refined to R values of 0.049 and 0.037, respectively. Crystals of 1 contain both of the paramagnetic (S = 5/2) mononuclear anions [Mn(SPh) 3 Br] 2- (3 a) and [Mn(SPh) 3 Cl] 2- (3b). The anions 3 a and 3 b are superimposed in an averaged unit cell and thus occupy crystallographically equivalent sites, the positions of the chlorine and bromine atoms being unresolved. The monohalide species are distributed statistically over 93% of the total anion positions. The remaining 7% are occupied by the dihalide species [Mn(SPh) 2 Br 2 ] 2- (4a) and [Mn(SPh) 2 BrCl] 2- (4b) in equal amounts. In all these cases the metal atoms exhibit a distorted tetrahedral stereochemistry. In crystals of 2 [Co 4 (SPh) 6 Cl 4 ] 2- anions (5) are observed which feature a {Co 4 S 6 Cl 4 } core consisting of a distorted (D 2d ) Co 4 tetrahedron inscribed in a moderately irregular S 6 octahedron defined by bridging S atoms of an adamantane type cage. The four chlorine atoms each bind to different Co atoms and define an outer Cl 4 tetrahedron, such that the overall symmetry of the {Co 4 S 6 Cl 4 } core comes close to T d . The results presented show that [M 3 (SPh) 3 Hal 6 ] 3- type species reported for M = Fe are not as readily formed for M = Mn and Co in methanolic solution, where other species are found instead. Physical properties such as solid state susceptibilities and 1 H NMR spectra confirm the identity of 1 and 2. Reactions of 4:1:2 molar ratio mixtures of NaSePh/MnCl 2 /Et 4 NCl and NaTePh/MnCl 2 /Et 4 NCl in methanol lead to [Et 4 N] 2 [Mn(SePh) 4 ] (6) and [Et 4 N] 2 [Mn(TePh) 4 ] (7). Both compounds crystallize in the monoclinic space group P2 1 /n with a = 16.162(4), b = 15.323(4), c = 16.949(4) Å, β = 91.28(2)°, Z = 4 for 6, and a = 16.367(6), b = 15.641(7), c = 17.220(7) Å, β = 92.00(3)°, Z = 4 for 7. Their structures were refined to R = 0.077 and 0.026, respectively. Four benzeneselenolate and benzenetellurolate ligands provide a slightly distorted tetrahedral coordination about the Mn(II) center for 6 and 7, respectively. The Mn–Se and Mn–Te distances average 2.567 and 2.742 Å, the Se– Mn– Se and Te–Mn–Te angles range from 99.1(1) to 124.2(1) and from 94.7(1) to 127.0(1)°, respectively.

Open Access June 2, 2014

Tetramethylthioharnstoff als Ligand in Übergangsmetallkomplexen: Redoxsubstitutionen mit dem Dithiobis(1,1,3_{,3-tetramethylformamidinium)-Kation Synthese und Kristallstrukturen von [Fe(SR)L₃]⁺BPh₄^-, [FeL₄]²⁺BPh₄^-)₂ und [Ru_Cl2(CO)₂L2] (R = 2,4,6-i-Pr₃C₆H₂; L = SC(NMe₂)₂) / Tetramethylthiourea as Ligand in Transition Metal Complexes:. Redox Substitution Reactions with the Dithiobis(1,1,3,3-tetramethylformamidinium) Cation Synthesis and Crystal Structures of [Fe(SR)L₃]⁺BPh₄^-, [FeL₄]²⁺(BPh₄^-)₂ and [RuCl₂(CO)₂L2] (R = 2,4,6-i-Pr₃C₆H₂; L = SC(NM_e2)₂)}

Ulrich Bierbach, Walter Barklage, Wolfgang Saak, Siegfried Pohl

Page range: 1593-1601

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Abstract

The oxidation of tetramethylthiourea (SC(NMe 2 ) 2 ,L) with HC1/H 2 O 2 yields dithiobis-(1,1,3,3-tetramethylformamidinium)dichloride, [{SC(NMe 2 ) 2 } 2 ] 2+ Cl 2 (1). Anions in 1 can be easily exchanged by tetraphenylborate to give [{SC(NMe 2 ) 2 } 2 ] 2+ (BPh 4 - ) 2 (2). The reaction of the neutral complex [Fe(SR) 2 L 2 ] (3) (R = 2,4,6-i-Pr 3 C 6 H 2 ) with 2 results in either partial or complete oxidation of the thiolate ligands, depending on the stoichiometric ratio of the reactants, and replacement by neutral ligands L. The cations [Fe(SR)L 3 ] + and [FeL 4 ]2+ were isolated as tetraphenylborate salts (4 and 5, respectively). [RuCl 2 (CO) 2 L 2 ] (6) was obtained by the reaction of dodecacarbonyltriruthenium with 1. In the course of the reaction ruthenium is oxidized and CO ligands are partially replaced by L and Cl - . The structures of 4, 5 and 6 were determined from single crystal X-ray diffraction data. 4: monoclinic, P 2 1 /n, a = 2272.1(2), b = 1009.1(1), c = 2533.4(2) pm, β = 96.96(1)°. V = 5765· 10 6 pm 3 , Z = 4, conventional R = 0.066. The cation of 4 shows a distorted tetrahedral coordination of Fe(II) with Fe–S thiolate 229.0(2) pm and Fe–S thiourea 237.6(2) pm (mean). 5: monoclinic, P 2 1 /n, a = 1153.2(1), b = 2913.8(1), c = 2019.1(1) pm, β = 92.84°. V = 6776.5 • 10 6 pm 3 , Z = 4, conventional R = 0.061. The cation of 5 possesses approximate D 2d symmetry with the central [FeS 4 ] tetrahedron compressed along the two-fold axis (Fe–S: 234.2 pm (mean)). 6: orthorhombic, P bcn, a = 847.9(2), b = 1442.2(3), c = 1660.1(3) pm. V = 2030.0· 10 6 pm 3 , Z = 4, conventional R = 0.037. The neutral complex cis, cis, trans-6 exhibits a distorted octahedral coordination of Ru(II) with thiourea ligands in trans position. 6 possesses C 2 symmetry. The S–Ru–S a angle was found to be 165.0°. The deviation from linearity is probably caused by the sterically hindered tetramethylthiourea ligands. The Ru–S bond length is 241.6(1) pm. Structural studies of geometrical parameters in tmtu complexes that are related to the nature of the M–S thiourea bond suggest, that 1,1,3,3-tetramethylthiourea (L) does not only function as a σ-donor but possibly also exhibits weak π-donor and π-acceptor properties, respectively. The exact type of bonding is determined by the nature and oxidation state of the metal centre.

Open Access June 2, 2014

Dimere und Ketten in Praseodym(III)acetat-sesquihydrat, Pr(CH₃COO)₃·1,5 H₂O / Dimers and Chains in Praseodymium(III)acetate-sesquihydrate, Pr(CH₃COO)₃ · 1.5 H₂O

Adalbert Lossin, Gerd Meyer

Page range: 1602-1608

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Abstract

Pr(CH 3 COO) 3 · 1.5 H 2 O crystallizes with the triclinic system, P̄1̄ (no. 2), Z = 4, a = 844.2(4), b = 1009.8(5), c = 1340.1(7) pm, α = 87.10(5), β = 76.25(6), y = 75.65(2)°, V m = 161.9(1) cm 3 /mol, R = 0.049, R w = 0.035. The crystal structure contains centrosymmetric dimers {[Pr(CH 3 COO) 4 (H 2 O)]-} 2 and one-dimensional chains ∞ 1 [Pr(CH 3 COO) 2 (H 2 O)] + along the [100] direction. Both units are built up by bridging acetate groups. The chains are linked by the dimers to layers parallel (101) sharing oxygen atoms. Crystal water molecules between these planes form hydrogen bonds to neighbouring layers.

Open Access June 2, 2014

Synthese und Charakterisierung achtgliedriger Cyclometallaphosphazene von Niob(V) und Titan(IV) sowie cyclischer und acyclischer Verbindungen von Molybdän(VI) mit Perfluoralkyl-Gruppen – Kristallstruktur von [Ph₂PNONbCl₃]₂ · 4 MeCN / Synthesis and Characterization of Eight-Membered Dimetallacyclophosphazenes with Niobium(V) and Titanium(IV) and Cyclic as well as Acyclic Compounds of Molybdenum(VI) Containing Perfluoroalkyl-Groups – X-Ray Crystal Structure of [Ph₂PNONbCl₃]₂·4MeCN

Petra Olms, Herbert W. Roesky, Klaus Keller, Mathias Noltemeyer

Page range: 1609-1613

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Abstract

Me 3 SiOPPh 2 NSiMe 3 (1) reacts with NbCl 5 and CpTiCl 3 to form the eight-membered ring compounds [Ph 2 PNONbCl 3 ] 2 (2) and [Ph 2 PNOTiClCp] 2 (3). The reaction of (C 2 F 5 ) 2 P(Cl)=NSiMe 3 (4) with MoO 2 Cl 2 and MoOCl 4 in CH 2 C1 2 quantitatively yields the compounds [MoOCl 3 -O-P(C 2 F 5 ) 2 =NSiMe 3 ] 4 (5) and (C 2 F 5 ) 2 P(Cl)=N-MoOCl 3 (6). Through recrystallization from MeCN, compound 2 has been isolated and characterized by means of X-ray analysis as the MeCN adduct 2 a.

Open Access June 2, 2014

Über Sulfide und Oxidsulfide des Samariums / On Sulfides and Oxysulfides of Samarium

Falk Lissner, Thomas Schleid

Page range: 1614-1620

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Abstract

Stoichiometric oxidation of SmCl 2 with sulfur in the presence of NaCl (evacuated silica vessel, 850 °C, 7 d) results in the formation of A—Sm 2 S 3 (orthorhombic, Pnma (no. 62), a = 737.64(5), b = 397.44(3), c = 1536.26(9) pm, Z = 4, R w = 0.017). In contrast, C—Sm 2 S 3 (cubic, I43 d (no. 220), a = 844.71(3) pm, Z = 5.333, R w = 0.017) is obtained upon reaction of the elements (Sm : S = 2 : 3) under otherwise analogous conditions. According to Sm 2.67 ⬜ 0.33 S 4 it represents a defect-variant of mixed-valence Th 3 P 4 -type Sm 3 S 4 (a = 852.39(3) pm, Z = 4, R w = 0.013) which forms whenever reducing tantalum is used as container material instead of silica tubing. Ubiquitous oxidic impurities thereby also react to yield the oxygen-poor oxysulfides Sm 10 S 14 O (tetragonal, 14 1 /acd (no. 142), a = 1485.96(4), c = 1974.04(8), Z = 8) and Sm 2 OS 2 (monoclinic, P2 1 /c (no. 14), a = 840.54(6), b = 706.20(5), c = 697.72(5) pm, β = 99.294(6)°, Ζ = 4, R w = 0.024) as by-products. Regardless of the container material, NaCltype SmS (cubic, Fm 3 m (no. 225), a = 596.04(3) pm, Z = 4) emerges as product from equimolar oxidation of samarium with sulfur. Reactions of Sm 2 S 3 with Sm 2 O 3 in 1: 2 molar ratios are suitable to produce Ce 2 O 2 S-type Sm 2 O 2 S (trigonal, P 3 ml (no. 164), a = 389.25(3), c = 671.18(7) pm, Z = 1) even in tantalum capsules at 850 °C when some NaCl is added as a flux.

Open Access June 2, 2014

Synthese, Kristallstruktur und ¹H-NMR-Spektrum des vierkernigen Komplexes [{LTi(OCH₃)}₂(μ-O)₄{Ti(acac)₂}2](C10₄)₂·2 H₂O / Synthesis, Crystal Structure and ¹H NMR Spectrum of the Tetranuclear Complex [{ LTi(OCH₃)}₂(μ-O)₄{Ti(acac)₂}₎₂](C10₄)₂·2 H₂O

Peter Jeske, Karl Wieghardt, Bernhard Nuber

Page range: 1621-1627

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Abstract

Reaction of LTiCl 3 (L = 1,4,7-trimethyl-1,4,7-triazacyclononane) in CH 3 OH with sodium 2,4-pentanedionate (acac) in the presence of air yields upon addition of NaClO 4 yellow crystals of the tetranuclear complex [{LTi(OCH 3 )} 2 (μ-O) 4 {Ti(acac) 2 } 2 ](ClO 4 ) 2 ·2H 2 O (1), the crystal structure of which has been determined. Crystal data: monoclinic, P2 1 /c, a = 9.563(4), b = 22.695(8), c = 13.842(5)Å, β = 93.69(3)°; Z = 2. The 400 MHz 1 H NMR spectrum shows that two different isomers with Δ, Λ -configuration at the Ti(acac) 2 (μ-O) 2 - and (δδδ) or (λλλ) conformation at the LTi(OCH 3 )(μ-O) 2 -fragment cocrystallize.

Open Access June 2, 2014

Studies with Alkylheteroaromatic Carbonitriles: A Novel Synthesis of Pyrazolo[2′,3′: 3,4]benzo[c]-1,2,4-triazine

Ahmed Hafez Hussein El-Ghandour, Mohamed Kamal Ahmed Ibrahim, Ibrahim Saad Abdel-Hafiz, Mohamed Hilmy Elnagdi

Page range: 1628-1632

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Abstract

A novel synthesis of derivatives of the title ring system by reacting methylpyrazolo[5,1-c]-1,2,4-triazin-6-carbonitriles (9) with sulphur and subsequent treatment of the resulting thienopyrazolotriazines with acetivated double bond system is described.

Open Access June 2, 2014

Struktur von Ferribactin aus Pseudomonas fluorescens ATCC 13525 [1] / The Structure of Ferribactin from Pseudomonasfluorescens ATCC 13525 [1]

U. Hohlneicher, R. Hartmann, K. Taraz, H. Budzikiewicz

Page range: 1633-1638

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Abstract

The primary structure of deferriferribactin 13525 which is produced by Pseudomonas fluorescens ATCC 13525 under iron deficient conditions was elucidated by 2 D-NMR-spectroscopic methods.

Open Access June 2, 2014

Cyclohex-2-en-l-ones in Heterocyclic Synthesis: Facile Synthesis of 5,6-Dihydrocoumarins, their Thio Analogues and their Corresponding Dehydrogenated Derivatives

G. A. M. Nawwar, B. M. Haggag, El-S. M. À. Yakout

Page range: 1639-1646

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Abstract

Novel synthesis of 5,6-dihydrocoumarins, their thioanalogues and their corresponding dehydrogenated derivatives utilizing substituted cyclohex-2-en-1-ones as starting components is reported.

Open Access June 2, 2014

NOTIZEN: Notiz zur vierfachen HX-Eliminierung aus peri-Tetrakis(chlormethyl)-aromaten unter Blitzvakuumthermolyse: Pyracylen / Note on Fourfold HX-Elimination from peri-Tetrakis(chloromethyl)-aromatic Compounds by Flash Vacuum Pyrolysis

Eckehard V. Dehmlow, Michael Fründ

Page range: 1647-1648

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Abstract

Gas phase pyrolysis in vacuo transforms 1,4,5,8-tetrakis(chloromethyl)naphthalene into pyracyclene.

Open Access June 2, 2014

Notizen: Synthese und Kristallstruktur von [{(CO)₅CrPhP}₂Se₃] / Synthesis and Crystal Structure of [{(CO)₅CrPhP}₂Se₃]

Kurt Merzweiler, Hans-Jörg Kersten

Page range: 1649-1652

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Abstract

The reaction of [{(CO) 5 Cr}PhPCl 2 ] with Se(SiMe 3 ) 2 leads to the formation of [{(CO) 5 CrPhP} 2 Se 3 ] (1). 1 contains a P 2 Se 3 -heterocycle which is coordinated to two {(CO) 5 Cr} units. 1 was characterized by NMR spectroscopy ( 31 P, 77 Se) and single crystal X-ray diffraction.

About this journal

Objective
Zeitschrift fuer Naturforschung B (ZNB) publishes novel research in all areas of inorganic chemistry, organic chemistry, and analytical chemistry. In particular, the journal focuses on solid state chemistry, coordination chemistry, main group element chemistry, synthetic organic chemistry, natural product chemistry and, to a lesser extent, on analytical chemistry. For more than 65 years Zeitschrift fuer Naturforschung B has been open to contributions from all fields of experimental and theoretical chemistry. Zeitschrift fuer Naturforschung B publishes 12 issues per volume/year. Sometimes double issues occur.

Topics

Solid state chemistry
Coordination chemistry
Main group element chemistry
Organic chemistry
Natural product chemistry

Article formats
Original (full) papers, research notes and preliminary communications, reports on specific research topics of current interest (reviews)

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Volume 47 Issue 11

Issue of Zeitschrift für Naturforschung B

Addition von O- und C-Nucleophilen an Ruthenium-Schwefeldioxid-Komplexe, Struktur von [cpRu(dppm)(SO2Et)] / Addition of O- and C-Nucleophiles to Ruthenium Sulfur Dioxide Complexes, Structure of [cpRu(dppm)(SO2Et)]

Abstract

3,5-Diphenyl-1,2-dithiolium-hydrogensulfat – Bildung und Struktur / 3,5-Diphenyl-1,2-dithiolium Hydrogensulphate – Synthesis and Structure

Abstract

Die Kristallstrukturen der Palladium(II)-Komplexe [Pd(CH3CN)4](BF4)2, [PdCl(μ2 -PPh2)(HPPh2)]2 · CH2Cl2 und [PdCl(HPPh2) {H(OPPh2)2}] / The Crystal Structures of the Palladium(II) Complexes [Pd(CH3CN)4](BF4)2, [PdCl(μ2-PPh2)(HPPh2)] · CH2Cl2, and [PdCl(HPPh2){H(OPPh2)2}]

Abstract

Preparation and Crystal Structures of Th5Fe19P12 and ThFe4P2

Abstract

Synthese von Phosphaalkenclustern durch reduktive Phosphinidenfragmentierung zweizähniger Halogenphosphane RXP— CH2 — PXR mit Fe2(CO)9 / Synthesis of Phosphaalkene Clusters by Reductive Phosphinidene Fragmentation of Bidentate Halogenphosphines RXP—CH2—PXR with Fe2(CO)9

Abstract

Photochemistry in Porous Materials, II / Photolysis of Benzoin Ethers in Silicalite

Abstract

Abstract

Gasphasen-Reaktionen, 91 [1-3]<br />Thermische und heterogen-katalysierte N2-Abspaltung aus Azo-Verbindungen R–N=N–R (R = CH3, C3H5, C6H5) / Gas Phase Reactions, 91 [1-3]<br />Thermal and Heterogeneously Catalyzed N2 Elimination of Azo-Compounds R–N=N–R (R = CH3, C3H5, C6H5)

Abstract

Unendliche Y2(H2O)10[C6(COO)6]-Ketten in Y2[C6(COO)6] · 14H2O / Infinite Chains of Y2(H2O)10[C6(COO)6] in Y2[C6(COO)6] · 14 H2O

Abstract

Crystal and Molecular Structure and Properties of Tetrasodium<br />[Bis { (µ-isothiocyanato-N,S)(N-salicylidene-β-alaninato) } dicuprate(II)] Dithiocyanate Tetrahydrate

Abstract

Nitrosolate und verwandte Verbindungen, XII Nitrosolatokomplexe von Silber(I) / Nitrosolates and Related Compounds, XII Nitrosolato Complexes of Silver(I)

Abstract

[Mn(SPh)3Cl]2-, [Mn(SPh)3Br]2-, [Mn(SePh)4]2-, [Mn(TePh)4]2-, and [Co4(SPh)6Cl4]2-: New Mixed Halide/Thiolate and Chalcogenolate Complexes of Manganese and Cobalt

Abstract

Abstract

Dimere und Ketten in Praseodym(III)acetat-sesquihydrat, Pr(CH3COO)3·1,5 H2O / Dimers and Chains in Praseodymium(III)acetate-sesquihydrate, Pr(CH3COO)3 · 1.5 H2O

Abstract

Abstract

Über Sulfide und Oxidsulfide des Samariums / On Sulfides and Oxysulfides of Samarium

Abstract

Synthese, Kristallstruktur und 1H-NMR-Spektrum des vierkernigen Komplexes [{LTi(OCH3)}2(μ-O)4{Ti(acac)2}2](C104)2·2 H2O / Synthesis, Crystal Structure and 1H NMR Spectrum of the Tetranuclear Complex [{ LTi(OCH3)}2(μ-O)4{Ti(acac)2})2](C104)2·2 H2O

Abstract

Studies with Alkylheteroaromatic Carbonitriles: A Novel Synthesis of Pyrazolo[2′,3′: 3,4]benzo[c]-1,2,4-triazine

Abstract

Struktur von Ferribactin aus Pseudomonas fluorescens ATCC 13525 [1] / The Structure of Ferribactin from Pseudomonasfluorescens ATCC 13525 [1]

Abstract

Cyclohex-2-en-l-ones in Heterocyclic Synthesis: Facile Synthesis of 5,6-Dihydrocoumarins, their Thio Analogues and their Corresponding Dehydrogenated Derivatives

Abstract

NOTIZEN: Notiz zur vierfachen HX-Eliminierung aus peri-Tetrakis(chlormethyl)-aromaten unter Blitzvakuumthermolyse: Pyracylen / Note on Fourfold HX-Elimination from peri-Tetrakis(chloromethyl)-aromatic Compounds by Flash Vacuum Pyrolysis

Abstract

Notizen: Synthese und Kristallstruktur von [{(CO)5CrPhP}2Se3] / Synthesis and Crystal Structure of [{(CO)5CrPhP}2Se3]

Abstract

Addition von O- und C-Nucleophilen an Ruthenium-Schwefeldioxid-Komplexe, Struktur von [cpRu(dppm)(SO₂Et)] / Addition of O- and C-Nucleophiles to Ruthenium Sulfur Dioxide Complexes, Structure of [cpRu(dppm)(SO₂Et)]

Preparation and Crystal Structures of Th₅Fe₁₉P₁₂ and ThFe₄P₂

Synthese von Phosphaalkenclustern durch reduktive Phosphinidenfragmentierung zweizähniger Halogenphosphane RXP— CH₂ — PXR mit Fe₂(CO)₉ / Synthesis of Phosphaalkene Clusters by Reductive Phosphinidene Fragmentation of Bidentate Halogenphosphines RXP—CH₂—PXR with Fe₂(CO)₉

Unendliche Y₂(H₂O)₁₀[C₆(COO)₆]-Ketten in Y₂[C6(COO)₆] · 14H₂O / Infinite Chains of Y₂(H₂O)₁₀[C₆(COO)₆] in Y₂[C₆(COO)₆] · 14 H₂O

[Mn(SPh)₃Cl]²-, [Mn(SPh)₃Br]^2-, [Mn(SePh)₄]^2-, [Mn(TePh)₄]^2-, and [Co₄(SPh)₆Cl₄]^2-: New Mixed Halide/Thiolate and Chalcogenolate Complexes of Manganese and Cobalt

Dimere und Ketten in Praseodym(III)acetat-sesquihydrat, Pr(CH₃COO)₃·1,5 H₂O / Dimers and Chains in Praseodymium(III)acetate-sesquihydrate, Pr(CH₃COO)₃ · 1.5 H₂O

Synthese, Kristallstruktur und ¹H-NMR-Spektrum des vierkernigen Komplexes [{LTi(OCH₃)}₂(μ-O)₄{Ti(acac)₂}2](C10₄)₂·2 H₂O / Synthesis, Crystal Structure and ¹H NMR Spectrum of the Tetranuclear Complex [{ LTi(OCH₃)}₂(μ-O)₄{Ti(acac)₂}₎₂](C10₄)₂·2 H₂O

Notizen: Synthese und Kristallstruktur von [{(CO)₅CrPhP}₂Se₃] / Synthesis and Crystal Structure of [{(CO)₅CrPhP}₂Se₃]