bluuebunny/crossref_metadata_2025 huggingface dataset:
Normalkoordinatenanalyse der 35Cl/37Cl-markierten Fluoro-Chloro-Platinate(IV), Cs2[PtFnCl6-n], n = 0-6 / Normal Coordinate Analysis of the 35Cl/37Cl Labelled Fluoro-Chloro-Platinates(IV), Cs2[PtF„Cl6-n, n = 0 – 6
Authors: Erlhöfer P. , Preetz W.
Published: March 2015

Normal coordinate analyses for all compounds of the two series Cs2[PtF„35Cl6-n] and Cs2[PtF„37Cl6-n], n = 0-6, including the geometric isomers for n = 2, 3, 4 have been performed, based on a general valence force field. The excellent agreement of calculated and observed frequencies confirms the assignments of the vibrational spectra. Due to the stronger trans influence of Cl compared to F in all asymmetric F–Pt–Cl axes the Pt–Cl bonds are strengthened and the Pt–F bonds are weakened, as indicated by valence force constants for Pt–Cl approximately 20% higher, for Pt–F 20% lower, compared with the values calculated for symmetric Cl–Pt–Cl and F–Pt–F axes, respectively. The contour of the Raman line ν2 (Eg, Oh) of Cs2[PtCl6] is explained by the superposition of the calculated spectra for the six most frequent isotopomers Cs2[Pt35Cln
37Cl6-n] present in mixtures with natural abundance of Cl isotopes (75,53% 35Cl, 24,47% 37Cl) by statistical distribution on the octahedron sites.
Intermetallische Verbindungen mit HgCl2-isosteren Anionen: Strukturelle und schwingungsspektroskopische Untersuchung von Na4HgP2, K4ZnP2, K4CdP2 und K4HgP2 / Intermetallic Compounds with HgCl2 Isoelectronic Anions: Crystal Structure and Vibrational Spectra of Na4HgP2, K4ZnP2, K4CdP2 and K4HgP2
Authors: Eisenmann B. , Somer M.
Published: March 2015

The new compounds Na4HgP2, K4ZnP2 and K4HgP2 are isotypic and crystallize in the rhombohedral system, space group R3m, Z = 3, with the lattice constants: Na4HgP2: a = 500.8(2) pm, c = 2544.7(8) pm, c/a = 5.081; K4ZnP2: a = 566.4(2) pm, c = 2610.1(8) pm, c/a = 4.608; K4HgP2: a = 567.1(2) pm, c = 2697.7(8) pm, c/a = 4.757. The crystal structure of the compound K4CdP2, formerly described in the monoclinic system (space group C2/m), has been revised (R3m, a = 568.1(2) pm, c = 2698.4(8) pm, c/a = 4.750). Linear units [P—T—P]4- with T = Zn, Cd, Hg, which are isoelectronic to the molecule HgCl2, represent the characteristic structure elements. The far infrared spectra are recorded and assigned on the basis of the [P—T—P]4- anions.
Struktur und Magnetismus stabiler Radikalkation-Salze: Ν,N′-Diethylchinoxalinium Tetraphenylborat im Vergleich mit Pyrazinium- und Phenazinium-Analogen / Structure and Magnetism of Stable Cation Radical Salts: N,N′-Diethylquinoxalinium Tetraphenylborate as Compared with Pyrazinium and Phenazinium Analogues
Authors: Hausen H.-D. , Kaim Wolfgang , Schulz Andreas , Roth Eberhard
Published: March 2015

Crystal and molecular structure analysis of N,N′-diethylquinoxalinium tetraphenylborate shows a virtually planar quinoxaline ring with 11 conjugated π electrons and approximately antiperiplanar ethyl groups. In comparison with the benzo-analogous phenazinium systems and the de-benzo derivative N,N′-diethylpyrazinium cation, the quinoxalinium species adopts an intermediate position in terms of intra- and intermolecular structural features. In particular, increasing benzanellation seems to favour a cation/anion approach for electrostatic reasons whereas the N—C bonds to the hyperconjugatively charge delocalizing alkyl groups increase due to peri interactions. Solid state magnetic and ESR measurements are compatible with the crystallographically determined structure.
A New Phosphorylation Method via O-Diethylboryl Intermediates
Authors: Dahlhoff Wilhelm V. , Taba Kalulu M.
Published: March 2015

Diphenylchlorophosphine and diethylchlorophosphite react with acetylacetone to generate intermediate phosphine enolates 3 which are quenched with O-diethylboryl derivatives and then oxidized with hydrogen peroxide to give diphenylphosphinates 4 and diethylphosphates 5.
Synthese hydroxylierter Binaphthochinone durch Amin/Hydroxyl-Austausch — Über die Umsetzung von 2,2′-Binaphthyl-1,4;1′,4′-dichinonen mit Piperidin / Synthesis of Hydroxylated Binaphthoquinones via Amine/Hydroxyl Exchange — On the Reaction of 2,2′-Binaphthyl-1,4;1′,4′-diquinones with Piperidine
Authors: Laatsch Hartmut
Published: March 2015

Bis-aminadducts 9 a/10 a, formed by reaction of piperidine with dimeric naphthoquinones of type 2, cyclize under acidic conditions yielding linear binaphtho[2,3-b;2′,3′-d]furan-5,13;7,12-diquinones 11. The latter are hydrolyzed easily, forming 3,3′-dihydroxylated 2,2′-binaphthoquinones (1) in good yield.
Notizen: Kristallstruktur von [MoCl2(NSN) · 2 THF]2; einem Metallaheterocyclus mit der NSN4--Einheit / Crystal Structure of [MoCl2(NSN) · 2 THF]2; a Metallaheterocycle with the NSN4- Unit
Authors: Hösler Klaus , Weller Frank , Dehnicke Kurt
Published: March 2015

The chlorothionitrene complex [Cl4Mo(NSCl)]2 reacts with N,N,N′-tris(trimethylsilyl)benzamidine in THF solution to form the heterocyclic complex [MoCl2(NSN) · 2 THF]2, which contains the [NSN]4-unit. The compound is characterized by IR spectroscopy and by an X-ray structure determination (Space group P2,/c, Z = 2, 1504 observed unique reflexions, R = 0.044. Lattice dimensions at 19°C: a = 1176.0(1), b = 1108.6(4), c = 1227.3(3) pm, β = 118.25(1)°). The compound forms centrosymmetric molecules [(THF)2Cl2Mo(NSN)2MoCl2(THF)2], in which the molybdenum atoms are members of a nearly planar Mo(NSN)2Mo eight-membered ring with bond lengths MoN 180.2 and 175.2 pm; NS 157.5 and 160.6 pm; the bond angle NSN is 108.3°, corresponding to a NSN4- unit.
Notizen: Identification of a Baker-type Mechanism in Additions to p-Nitrophenyl Isothiocyanate in Diethyl Ether Solution
Authors: Satchell Derek P. N. , Satchell Rosemary S.
Published: March 2015

Kinetic evidence is presented which strongly suggests that in the diethyl ether solution the aminolysis of p-nitrophenyl isothiocyanate proceeds via a mechanism involving a 1:1-addition intermediate which undergoes catalyzed prototropic rearrangement to the product (Baker-type mechanism).
Li7O2Br3 — Eine weitere Strukturvariante der neuen Alkalimetallchalkogenidhalogenid-Perowskite / Li7O2Br3 — A Further Structure Variant of the New Alkali Metal Chalcogenide Halide Perovskites
Authors: Wortmann Regina , Sitta Stephan , Sabrowsky Horst
Published: March 2015

The colourless compounds Li3OBr and Li7O2Br3 have been prepared and characterized by X-ray diffraction techniques. Li3OBr crystallizes in a cubic primitive lattice (Pm3m) with a = 405.6(1) pm (Z = 1). The structure is related to the anti-perovskite type. Li7O2Br3 crystallizes in a tetragonal bodycentered lattice (I4/mmm) with a = 403.5(1) pm, c = 2161(1) pm (Z = 2) and is isotypic to Sr3Ti2O7.
Substitutionsreaktionen am Tetrafluorotantal-Komplex (η5-C5Me5)—TaF4 / Substitution Reactions at the Tetrafluorotantalum Complex (η5-C5Me5)—TaF4
Authors: Roesky Herbert W. , Schrumpf Frank , Noltemeyer Mathias
Published: March 2015

Cp*TaF4 (1) (Cp* = η5-C5Me5) reacts with lithium salts of benzamidines or 1,3-diketones to form hexa-coordinated complexes of composition Cp*TaF3[(Me3SiN)2CPh] (2), Cp*TaF3[(Me3SiN)2C(p-CF3C6H4)] (3) and Cp*TaF3(O=CPhCH=CPhO) (4). The reactions proceed under elimination of LiF. The X-ray crystal structure of Cp*TaF3(O=CPhCH=CPhO) (4) has been determined shows tantalum to have a distorted octahedral environment, if the Cp* ligand is considered to occupy one coordination site.
Outer-sphere-CT-Wechselwirkungen zwischen einem organischen π-Radikaldikation und Hauptgruppenelement-Hexahalogenat-Komplexen / Outer-Sphere-CT-Interactions between an Organic π-Radical Dication and Main-Group Hexahalogenate Complexes
Authors: Weiss Robert , Grimmeiss Andreas M. H.
Published: March 2015

1:1-Electrolytes of the type [tris(dimethylamino)cyclopropendiylium]2+ElX6
2- have been synthesized for the first time (El = Sn, Te; X = Cl, Br). Analysis of their UV spectra points to a novel OSCT-interaction within these ion pairs in which the complex anion acts as the donor. With 48-electron systems as SnX6
2- the bromo complex is the better donor than the chloro complex whereas with 50-electron systems TeX6
2- the reverse behaviour is observed. These contrasting tendencies can be explained by a simple MO model, according to which SnX6
2- anions interact with the organic acceptor via a HOMO of tlu- symmetry, whereas anions of the type TeX6
2- employ their alg*-HOMO.
9-Aminofluorenium Cations: A New Group of anti-Aromatic Molecules
Authors: Tyutyulkov N. , Kavrakova I. , Nikolov P. , Dietz F.
Published: March 2015

Quantum-chemical and spectral studies on the protonated form of fluorenone-anil show that this compound has anti-aromatic character. Its real structure should be considered as: 9-amino derivative of the anti-aromatic fluorenium cation.
Neuartige basische Liganden für die homogenkatalytische Methanolcarbonylierung, XXIV [1]. Rhodium-Komplexe mit (Ether-Phosphan)-Liganden unterschiedlicher Basizität und ihr Einfluß bei der Methylwanderung / Novel Basic Ligands for the Homogenous Catalytic Methanol Carbonylation, XXIV [1]. Rhodium Complexes with (Ether-Phosphane) Ligands of Different Basicity and their Influence on the Methyl Migration
Authors: Lindner Ekkehard , Norz Hubert
Published: March 2015

[(COD)Rh(Cl)(P1∼O)] (3) is obtained from [µ-ClRh(COD)]2 (1) and the (ether-phosphane) ligand P1∼O (2) [P1∼O = Ph2PCH2CH2OCH3]. 3 reacts with AgSbF6 to form the cationic η2-Pl͡ O rhodium complex [(COD)Rh(P1 ͡ O)][SbF6] (4). Addition of another ligand P2∼O (5) [P2∼O = Pr2PCH2C4H7O] to 4 affords the bis(ether-phosphane)rhodium complex

[(COD)Rh(P1∼O)(P2∼O)][SbF6] (6) with two different ether-phosphanes. In 6 COD is displaced by CO to give [trans-(P1∼O)(P2∼O)Rh(CO)3][SbF6] (7). The 31Ρ{1H} NMR spectrum of 7 shows a temperature dependence. When a THF solution of compound 7 is flushed with argon it undergoes elimination of carbon monoxide to form [trans-(P1∼O)(P2 ͡ O)Rh(CO)][SbF6] (10), containing a bidentate coordinated P2∼O ligand (5). The reaction is reversible. Oxidative addition of CH3I to 10 results in the formation of a 1:1 mixture of the acyl complexes [cis-(P1 ͡ O)(P2͡ O)Rh(I)(C(0)CH3)][SbF6] (8) and [cis-(P1͡ O)(P2͡ O)Rh(I)(C(O)CH3)][SbF6] (9), the reactive intermediate [trans-(P1∼O)(P2͡ O)Rh(I)(CH3)(CO)][SbF6] (11) not being observed. Formation of either 8 or 9 depends on the S or R configuration of the asymmetric C-atom in 5. On cleaving one or two Rh–O bonds the back reaction to 7 occurs.
Synthese und Kristallstruktur von PPh4[ReF2Cl2(N2S2)] / Synthesis and Crystal Structure of PPh4[ReF2Cl2(N2S2)]
Authors: Vogler Stefan , Dehnicke Kurt , Hiller Wolfgang
Published: March 2015

PPh4[ReF2Cl2(N2S2)] has been prepared by the reaction of PPh4[ReCl4(NSCl)2] · CH2Cl2 with sodium fluoride in acetonitrile suspension. The compound forms black crystals, which were characterized by IR spectroscopy as well as by an X-ray structure determination.

Space group P21/c, Z = 4, 2525 observed unique reflexions, R = 0.053. Lattice dimensions at 20°C: a = 1277.4(3), b = 713.2(3), c = 2860.8(4) pm. β = 97.20(3)°. The compound consists of PPh4
+ and [ReF2Cl2(N2S2)]- ions, in which the rhenium atom is surrounded octahedrally by two fluorine atoms, two chlorine atoms, and by the nitrogen atoms of a ReN2S2 five-membered ring, the fluorine ligands being in trans position to the N atoms. The bond lengths ReN (172; 177 pm) and NS (155; 160 pm) are in the range of double bonds, the S—S bond is relatively long (243 pm).
Kationische Schwefeldioxid-Komplexe des Eisens und Rutheniums vom Halbsandwich-Typ [1] / Cationic Halfsandwich-Type Sulfur Dioxide Complexes of Iron and Ruthenium [1]
Authors: Schenk Wolfdieter A. , Karl Ute , Horn Michael R.
Published: March 2015

Cationic halfsandwich-type complexes of sulfur dioxide, [C5R5M(PR3)2(SO2)]+ (R = H, Me, M = Fe, Ru, (PR3)2 = mono- or bidentate phosphorus ligands) and [C5Me5Fe(CO)(PR3)(SO2)]+, are obtained by ligand exchange from labile cationic (M = Fe) or neutral (M = Ru) precursors. The new compounds are characterized by IR, 1H13
1H, 13C and 31P NMR spectroscopy. Their stability increases with increasing electron density at the metal.
Kristall- und Molekülstruktur des dimeren 1,2-Dioxyphenylen-siliciumdichlorids / Crystal and Molecular Structure of the Dimeric 1,2-Dioxyphenylene Silicondichloride
Authors: Hönle Wolfgang , Dettlaff-Weglikowska Urszula , Walz Leonhard , von Schnering Hans Georg
Published: March 2015

1,2-Dioxyphenylene silicondichloride is formed as a dimer from SiCl4 and catechol C6H4(OH)2 as the first reaction product. The compound melts at 413 K, yielding a viscous liquid which recrystallizes very slowly presumable under the formation of the monomer. 1,2-Dioxyphenylene silicondichloride crystallizes as a dimer in the space group P21/a (No. 14) with a = 1308.5(8) pm, b = 735.8(5) pm, c = 889.6(5) pm, β = 110.02(5)°, Z = 4 formula units. Silicon is tetrahedrally coordinated by two oxygen and two chlorine atoms with the mean bond lengths d̄(Si—O) = 160.7 pm and d̄(Si—Cl) = 200.7 pm. The bond angles at the Si atom range from 104.4 to 112.6° (endocyclic O—Si—O = 110.3°) and the bond angles ∢ (Si—O—C) are 131.4 and 135.9°, respectively. The results are discussed together with data of related compounds.
Photochemical Reactions of Primary Aromatic Amines with Chloromethanes in Solution. I. Spectrochemical Studies
Authors: Boszczyk Wojciech , Latowski Tadeusz
Published: March 2015

Interactions were studied of aniline, 4-methoxyaniline and 4-ethoxyaniline with tetrachloromethane, chloroform and dichloromethane in their ground and first excited singlet states. Stability constants of the complexes of these amines with the chloromethanes in cyclohexane were determined as well as their quantum yields of fluorescence in this solvent. The quenching of fluorescence of aniline and its derivatives by the chloromethanes was ascertained and characterized. Quantum yields of the formation of hydrogen chloride, ψΗCl, were measured during photochemically induced reaction of the amines in tetrachloromethane, chloroform and dichloromethane.
Photochemical Reactions of Primary Aromatic Amines with Chloromethanes in Solution. II. The Products and Mechanisms of Partial Reactions of Aniline in Tetrachloromethane, Chloroform and Dichloromethane
Authors: Boszczyk Wojciech , Latowski Tadeusz
Published: March 2015

Major products of photochemical reactions of aniline in tetrachloromethane, chloroform and dichloromethane have been isolated and identified. The mechanisms of partial reactions have been discussed.
Zur Reaktion von [MCl2(PR3)2] (M = Ni, Pd) mit E(SiMe3)2 (E = S, Se) Die Kristallstrukturen von [Ni3S2Cl2(PPh3)4], [Pd3S2Cl2(PPh3)4], INi3Se2(SeSiMe3)2(P(C2H4Ph)3)4] und [Pd3Se2(SeSiMe3)2(PPh3)4] / Reaction of [MCl2(PR3)2] (M = Ni, Pd) with E(SiMe3)2 (E = S, Se) The Crystal Structures of [Ni3S2Cl2(PPh3)4], [Pd3S2Cl2(PPh3)4], [Ni3Se2(SeSiMe3)2(P(C2H4Ph)3)4] and [Pd3Se2(SeSiMe3)2(PPh3)4]
Authors: Fenske Dieter , Fleischer Holm , Krautscheid Harald , Magull Jörg
Published: March 2015

[MC12(PR3)2] (M = Ni, Pd) reacts with E(SiMe3)2 (E = S, Se) to form triangular clusters, [Ni3S2Cl2(PPh3)4] (1), [Pd3S2Cl2(PPh3)4] (2), [Ni3Se2(SeSiMe3)2(P(C2H4Ph)3)4] (4) and [Pd3Se2(SeSiMe3)2(PPh3)4] (3). 1-4 have been characterized by X-ray crystal structure analysis. All these compounds contain a triangular M3-core, which is capped by two μ3-E-ligands (E = S in 1, Se in 3 and 4).
Oxidationsreaktionen an ΧnB6Η6-n
2-, Χ = Cl, Br, I; n = 1-6 und Kristallstrukturen von [(n-C4H9)4N]B6I6 und [(n-C4H9)4N]2B6I6 / Oxidation Reactions on XnB6H6-n
2-, X = Cl, Br, I; n = 1-6, and Crystal Structures of [(n-C4H9)4N]B6I6 and [(n-C4H9)4N],B6I6
Authors: Heinrich A. , Keller H.-L. , Preetz W.
Published: March 2015

By cyclic voltammetry investigations in acetonitrile solution it has been shown, that the halogenohydrohexaborates X„B6H6-n
2-, X = Cl, Br, I; n = 1-6, undergo a one-electron oxidation to form the corresponding radical anions. The reactions are completely reversible only for the perhalogenated ions B6X6
2- and for trans-Br4Β6Η2
2-. The oxidation by Ce(IV) in CH3CN yields deep blue B6I6, orange B6Br6- and yellow green B6Cl6-, characterized by their UV-VIS, IR/Raman spectra and by magnetic measurements. The crystal structures of the paramagnetic, air-stable, blue-black [(n-C4H9)4N]B6I6 (I) and the diamagnetic, colourless [(n-C4H9)4N]2B6I6 (II) were determined from single crystal X-ray diffraction analyses. I is monoclinic, space group P21/c, with a = 14.398(7), b = 14.638(3), c = 16.511(6) Å, β = 109.24(1)° (at —50°C), containing two crystallographically independent centrosymmetric B6 entities, which are strongly distorted with B— B bond lengths between 1.63 and 1.91 and I— I between 2.02 and 2.22 A. II is monoclinic, space group P21, with a = 11.246(3), b = 15.576(4), c = 14.900(4) Å, β = 92.10(1)° (at 23 °C) and contains nearly regular octahedral anions with bond lengths B—B 1.64-1.68 and B—I 2.17-2.21 A.
Synthese und Reaktivität von Alkinyl-substituierten Titanocen-Komplexen / Synthesis and Reactivity of Alkyne Substituted Titanocene Complexes
Authors: Lang Heinrich , Seyferth Dietmar
Published: March 2015

(η5-C5H5)2TiCl2 (1a) reacts with one equivalent of Li–C≡C–Si(CH3)3 to yield the mono alkynyl-substituted titanocene complex η5C5H5)2,Ti(Cl)[C≡C–Si(CH3)3] (2). The reaction of 2 with another equivalent of Li–C≡C–Si(CH3)3 gives the disubstituted compound (η5-C5H5)2Ti[C≡C–Si(CH3)3]2 (3f).

In general, complexes of the type (η5-C5H4R)2Ti(C≡C–R′)2 (R = H, CH3, Si(CH3)3; R′ = C6H5, C2H5, nC3H7, nC4H9, ′C4H9, Si(CH3)3), 3-5, can be prepared by the reaction of η5-C5H4R)2,TiCl2 (1) and two moles of E–C≡C–R′ (E = BrMg, Na, Li; R, R′ = see above) to give the compounds 3-5 in yields of up to 95%. The reaction of 2-5 with X2 or HX yields the appropriate compounds η5-C5H4R)2TiX2 (X = F, Cl, Br) and H–C≡C–R′ or X–C≡C–R′.
Eisen- und Cobaltkomplexe mit Schwefelliganden: Darstellung und Kristallstrukturen von [Me4N][FeCl{S2P(OMe)2}2], [Me4N][CoCl{S2P(OMe)2}2], [Et4N][FeCl{S2P(p-C6H4Me)2}2], [Et4N]2[FeCl{ S2PS(OMe) } 2] und [Fe { S2P(OMe)2 }3] / Iron and Cobalt Complexes with Sulfur-Containing Ligands: Preparation and Crystal Structures of [Me4N][FeCl{S2P(OMe)2}2],[Me4N][CoCl{S2P(OMe)2}2], [Et4N][FeCl{S2P(p-C6H4Me)2}2], [Et4N]2[FeCl{S2PS(OMe)}2] and [Fe{S2P(OMe)2}3]
Authors: Kirschbaum Kristin , Bönnighausen Uta , Gesing Ewald , Greiwe Klaus , Kuhlmann Ulrich , Strasdeit Henry , Krebs Bernt , Henkel Gerald
Published: March 2015

The reaction systems MCl2/K{S2P(OMe)2} (M = Fe(II), Co(II)), FeCl2/Na{S2S2P(p-C6H4Me)2}, and FeCl3/K2{S2PS(OMe)} in methanol afford the mononuclear complexes [FeCl{S2P(OMe)2}2]-, [CoCl{S2P(OMe)2}2]-, [FeCl{S2P(p-C6H4Me)2}2]-, and [FeCl{S2PS(OMe)}2]2-, which were isolated as salts [Me4N][FeCl{S2P(OMe)2}2] (1), [Me4N][CoCl{S2P(OMe)2}2] (2), [Et4N][FeCl{S2P(p-C6H4Me)2}2] (3) and [Et4N]2[FeCl{S2PS(OMe)}2] (4), respectively. Crystals of [Me4N][MCl{S2P(OMe)2}2] are triclinic, space group P 1 (Z = 2): Fe(II), a = 7.165(3), b = 8.628(3), c = 16.526(6)Å, α = 83.98(3), β = 85.32(3), γ = 89.80(3)°; Co(II), a = 7.164(2), b = 8.612(2), c = 16.504(4)Å, α = 84.59(2), β = 84.63(2), γ = 89.41(2)°. The structures of 1 and 2 were refined to R (Rw) = 0.034 (0.043) and 0.028 (0.032), respectively. Compound 3 is monoclinic, space group C2/c, Z = 4 with a = 23.831(5), b = 10.536(3), c = 17.133(4)Å, β = 114.43(3)°. Its structure was refined to R (Rw) = 0.046 (0.052). 4 crystallizes in the orthorhombic space group Pccn with a = 13.310(2), b = 12.982(2), c = 18.968(3) Å, and Z = 4. The refinement converged to R (Rw) = 0.042 (0.039). The anions of the compounds 1—4 contain five-coordinated metal centers which reside in distorted trigonal-bipyramidal (1, 2, and 3) or square pyramidal (4) S4Cl-environments. The neutral complex [Fe{S2P(OMe)2}3] (5) with six-coordinated metal sites was isolated from the reaction system FeCl3/K{S2P(OMe)2} in CH2Cl2. 5 is monoclinic, space group C 2/c (Z = 4) with a = 14.211(2), b = 11.115(2), c = 12.823(2) Å, β = 97.23(1)°. The refinement converged to R (Rw) = 0.022 (0.031). The anions of 1, 2, and 3 represent the first examples of structurally defined mononuclear Fe(II) and Co(II) complexes containing 1,1-dithiolate groups and halide ions simultaneously.
Reaktive E=C(p – p) π-Systeme, XXI [1] / Reactive E=C(p – p)π-Systems, XXI [1]
Authors: Grobe Joseph , Lange Gudrun , Le Van Duc
Published: March 2015

1λ3,3λ3-Diphosphanes of the type R2PCF2P(H)CF3 [R = Me (3), Et (5), Cyclohexyl (6), Ph (7)] are formed in acceptable yields (40-75%) by reacting perfluoro-2-phosphapropene F3CP=CF2 (1) with the corresponding secondary phosphanes R2PH. By reaction with sulfur, compounds 3, 5 and 7 selectively yield the corresponding monosulfur derivates R2P(S)CF2P(H)CF3 [R = Me (8), Et (9), Ph (10)]. Treatment of 3 or 7 with dimethylamine (molar ratio 1/2) leads via HF elimination and addition of Me2NH to the aminophosphanes R2PCHFP(NMe2)CF3 [R = Me (11), Ph (12)]. In a similar procedure HF has been eliminated from 3 by 1,4-diazabicyclo[2.2.2]octane (DABCO), and on addition of methanol or ethanol to the 1,3-diphosphapropene intermediate, the alkoxy compounds Me2PCHFP(OR)CF3 [R = Me (13), Et (14)] have been obtained.
Methylierung 3,3′-dihydroxylierter 2,2′-Binaphthyl-1,4;1′,4′-dichinone / Methylation of 3,3′-Dihydroxylated 2,2′-Binaphtho-1,4;1′,4′-quinones
Authors: Laatsch Hartmut
Published: March 2015

Monomeric hydroxy-p-quinones (1) are in equilibrium with the corresponding o-quinones (2) and on methylation, a mixture of both isomeric ethers is obtained. In contrast, dimeric hydroxynaphthoquinones with the 3 a-skeleton in treatment with diazomethane are yielding only p-quinone ethers of type 3b.
Synthese und Kristallstruktur von Te4
2+(WCl6-)2 / Synthesis and Crystal Structure of Te4
2+(WCl6
-)2
Authors: Beck Johannes
Published: March 2015

WCl6 reacts with two equivalents of tellurium in a sealed evacuated ampoule in the temperature range from 170 to 190 °C to give Te4
2+(WCl6
-)2. Under the same conditions with one equivalent of tellurium WCl5 yields Te4
2+(WCl6
-)2 and WCl4. Te4(WCl6), formes black crystals, which are sensitive to moist air. It decomposes at temperatures above 300° C to Te and WCl6. The crystal structure determination (lattice constants a = 638.9(1), b = 753.2(2), c = 1102.0(5) pm, α = 101.19(2)°, β = 102.85(2)°, γ = 90.21(1)°, Z = 1, triclinic space group P 1̄, 3572 unique reflections for 82 parameters, final R = 0.026) shows the nearly ideal square Te4
2+ cation with Te–Te distances of 268.8 and 268.7 pm and markedly distorted WCl6
– octaedra with W–Cl bond length from 227.5 to 237.3 pm. The structure involves interionic Te–Cl contacts as short as 319 pm.
Synthese eines kubanartigen Clusterchelats mit einem [Mo3SnS4]6+-Kern / Synthesis of a Cubane-Type Cluster Chelate with a [Mo3SnS4]6+ Core
Authors: Keck Helmut , Kruse Andreas , Kuchen Wilhelm , Mootz Dietrich , Wiskemann René , Wunderlich Hartmut
Published: March 2015

The cubane-type diamagnetic cluster Mo3SnS4(Et2PS2)6 (1) is obtained by reaction of the “incomplete” cubane Mo3S4(Et2PS2)4 either with tin powder and Et2P(S)—S—S—P(S)Et2 or with bis(diethyldithiophosphinato)tin(II). While the Sn atom and two of the Mo atoms in the core are chelated by Et2PS2⁻, the remaining Mo atom serves as a bridgehead for three dithiophosphinato-ligand bridges to the other metals. 1 crystallizes in the orthorhombic space group Pbca with Z = 8 and lattice parameters a = 2240( 1), b = 2261 ( 1), c = 2401 (1) pm.
2-Hydroxyimino-1,3-indandione Salts with Ammonia and Amines
Authors: Minchev St. , Enchev V. , Nedev H.
Published: March 2015

The preparation, structure and spectral characteristics of intensely colored salts of 2-hydroxyimino-1,3-indandione with ammonia and amines are described. The crystallization of the salts takes place with a high yield. All the salts fluoresce in DMSO. MNDO calculations show that the formation of an anion from 2-hydroxyimino-1,3-indandione is associated with substantial alterations in the nitroso group.
2,3,9-Trihydroxyphenazin-l-carbonsäure – ein unter Berylliumeinwirkung gebildetes neues Phenazinderivat aus Pseudomonas fluorescens [1] / 2,3,9-Trihydroxyphenazine- l -carboxylic Acid — a New Phenazine Derivative from Pseudomonas fluorescens Grown under Beryllium Stress [1]
Authors: Taraz K. , Schaffner E. M. , Budzikiewicz H. , Korth H. , Pulverer G.
Published: March 2015

In addition to phenazine, phenazine-1-carboxylic acid, phenazine-1,6-dicarboxylic acid and 2,9-dihydroxyphenazine-1-carboxylic acid a new compound, viz. 2,3,9-trihydroxyphenazine-1-carboxylic acid could be isolated from the culture medium of Pseudomonas fluorescens grown under iron deficiency with beryllium added to the culture medium. Its structure elucidation is described.
Notizen: Synthesis and Magnetic Properties of Oxo-Bridged Tetranuclear Iron(III) and Manganese(III) Complexes
Authors: Nishida Yuzo , Nasu Miyuki , Tokii Tadashi
Published: March 2015

New tetranuclear iron(III) and manganese(III) complexes with 1,4-bis[N,N-bis(2-benzimidazolylmethyl)amino]butane, and their hexane derivatives were prepared. Magnetic measurements suggest that these have an oxo-bridged structure of Toftlund type.
Hochdruckumwandlungen von Cer(III)Orthovanadat(V), CeVO4 / High-Pressure Transformations of Cerium(III) Orthovanadate(V), CeVO4
Authors: Range Klaus-Jürgen , Meister Helmut , Klement Ulrich
Published: March 2015

The polymorphism of CeVO4 was investigated at high pressures and temperatures in a Belttype high-pressure apparatus. In addition to the normal-pressure modification CeVO4— I with zircon-type structure two high-pressure modifications have been found, viz. monazite-type CeVO4—II and scheelite-type CeVO4—III. CeVO4—II is stable between 1 bar and 30 kbar at 1300 °C. Its region of existence decreases rapidly at lower temperatures. From the observed p,T-relations for the I-II and I-III transformations a triple point CeVO4—I,II,III at about 27 kbar, 500 °C can be estimated. For kinetic reasons, however, the experimental determination of phase relations becomes difficult at temperatures below 600 °C.

The crystal structures of CeVO4— I and —II have been refined from single-crystal data. Crystallographic data for the three modifications are given and discussed (CeVO4—I: I 41/amd, a = 7.383(1)Å, c = 6.485(1)Å, Z = 4; CeVO4—II: P21/n, a = 7.003(1)Å, b = 7.227(1)Å, c = 6.685(1)Å, β = 105.13(1)°, Z = 4; CeVO4—III: I 41/α, a = 5.1645(2)Å, c = 11.8482(7)Å, Z = 4).
Darstellung und Kristallstruktur von Rubidiumdicyanoaurat(I), RbAu(CN)2 / Synthesis and Crystal Structure of Rubidium Dicyanoaurate(I), RbAu(CN)2
Authors: Schubert R. J. , Range K.-J.
Published: March 2015

Using a modified cyanide process RbAu(CN)2 was synthesized by the reaction of gold powder with RbOH, O2 and liquid HCN. The colourless crystals are monoclinic, space group C2/c, with a = 18.450(3), b = 8.998(2), c = 13.418(2) Å, β = 108.0(9)° and Z = 16. The structure could be solved by Patterson and standard direct methods and refined to R = 0.035 and Rw = 0.034, respectively, for 857 absorption-corrected unique reflections. The structure comprises layers of linear [Au(CN)2]- groups, in which gold atoms are arranged in four- and eightmembered rings. The stacking of the layers with a sequence ABAB creates different kinds of holes which are occupied by the rubidium ions.
Reaktionen an komplexgebundenen Liganden, XL+ Azido-Komplexe mit niedrigvalenten Zentralmetallen: Synthese und Eigenschaften von (NEt4)[ArenCr(CO)2N3] (Aren = Mesitylen, Terephthalsäuredimethylester) sowie (NEt4)[CpRe(CO)2N3] und Umwandlung in N2-Komplexe / Reactions of Complex Bound Ligands, XL+
Azido Complexes with Low Valent Metal Centers: Synthesis and Properties of (NEt4)[AreneCr(CO)2N3] (Arene = Mesitylene, Terephthalic Acid Dimethyl Ester) and (NEt4)[CpRe(CO)2N3] and Conversion into N2 Complexes
Authors: Sellmann Dieter , Holzmeier Adelgunde
Published: March 2015

(NEt4)[MesCr(CO)2N3] (1) (Mes = mesitylene), (NEt4)[TDMCr(CO)2N3] (2) (TDM = terephthalic acid dimethyl ester) and (NEt4)[CpRe(CO)2N3] (3) (Cp = η5-cyclopentadienyl) were obtained from the corresponding [AreneCr(CO)2THF] complexes and [CpRe(CO)2THF], respectively, and NEt4N3. 1 and 2 decompose above —10 °C and 3 is light sensitive. Attempts to obtain new nitrogen ligands which are unstable in free state by reacting the azido complexes with H+, Me+ and NO+, respectively, led preferably to the N2 complexes [AreneCr(CO)2N2] and [CpRe(CO)2N2], respectively, and decomposition products.
Normalkoordinatenanalyse und Frequenzberechnungen für die isotopomeren closo-Hydrohexaborate 11Bn
10B6-nH6
2- , n = 0 – 6 / Normal Coordinate Analysis and Frequency Calculations of Isotopomeric closo-Hydrohexaborates 11Bn
10B6-nH6
2- , n = 0 – 6
Authors: Thesing J. , Preetz W.
Published: March 2015

Normal coordinate analyses for the ten isotopomers Cs2
11Bn
10B6-nH6, n = 0 — 6, including the pairs of geometric isomers for n = 2, 3, 4 have been performed, based on a general valence force field. The shift of the bands as well as the splitting of degenerate modes by lowered symmetry due to exchange of 10B by 11B or H by D is exactly calculated by a set of six force constants. The characteristic band patterns observed in the IR and Raman spectra of Cs2B6H6 with natural abundance of B isotopes (80.22% 11B, 19.78% 10B) measured at 10 K are explained by the superposition of the calculated spectra of the different isotopomers present, according to their statistical frequency distribution. The calculated atomic displacements and the potential energy distribution on the symmetry coordinates reveal only a small coupling (PED < 10%) between the cage (in-phase displacements of H and B) and substituent vibrations (anti-phase motions of B and H). Based on the normal coordinate analyses previously obtained assignments for several bands are revised.
Synthese und Kristallstruktur von [Ag(PhN3C6H4N3(H)Ph)]4, einem tetrameren Ag(I)-Komplex mit überbrückenden Bistriazenido-Liganden / Synthesis and Crystal Structure of [Ag(PhN3C6H4N3(H)Ph)]4, a Tetrameric Ag(I) Complex with Bridging Bistriazenido Ligands
Authors: Hörner Manfredo , Pedroso Antônio Gilberto , de Menezes Peixoto Carlos Roberto , Beck Johannes
Published: March 2015

[Ag(PhN3C6H4N3(H)Ph)]4 is obtained by the reaction of AgNO3 with [PhN3C6H4N3(H)Ph)]Na in tetrahydrofurane in form of brown crystals. The crystal structure determination (orthorhombic space group Pbcn, a = 1989.7(8), b = 1917.5(3), c = 1767.1(4) pm, Z = 4, 1784 reflections for 200 parameters, final R = 0.059) shows the complex to be isotypic to the previous described copper analogue. The complex is built of a rhombus of four silver atoms and four bridging bistriazenido units. One nitrogen atom of a neutral nitrogen chain completes the coordination sphere of each silver atom to a distorted trigonal bipyramidal environment of two other silver atoms and three nitrogen atoms. The Ag–Ag distances are in the range from 279.9 to 310.3 pm, the Ag–N distances from 217 to 236 pm.
Synthese und Photoisomerisierung von sterisch gehinderten 2,6-Dialkylpyridin-N-oxiden / Synthesis and Photoisomerization of Sterically Hindered 2,6-Dialkylpyridine-N-oxides
Authors: Weber Horst , Rohn Thomas
Published: March 2015

Synthesis of the new sterically hindered pyridine-1-oxides 2c and 6a–c is described. Copper(II)-catalyzed photolysis of 2 and 6a in aqueous medium provides only small amounts of 2-acylpyrroles 8 and 10a together with by-products. Exclusive formation and better yields of 10 can be received upon irradiation of 6 in none protic solvents at low temperature. Introduction of bulky substituents as in 6 failed to stabilize any of the postulated intermediates in order to be identified during photoreaction. It is assumed that the high rate of polymerization is caused by unstable 1,3-oxazepines like 13.
Notizen: A CNDO/2 Study of the Homoconjugation Energies of 4-Substituted Pyridine N-Oxides
Authors: Chmurzyński Lech , Liwo Adam
Published: March 2015

Homoconjugation energies in vacuo have been calculated for pyridine N-oxide (PyO) and its 4-methyl- (4 PicO) and 4-nitro- (4-NO2PyO) derivatives with the use of the CNDO/2 method. Comparison with the experimental homoconjugation constants in some aprotic solvents reveals the opposite order of the stability of homocomplexes than could be expected based on the calculated homoconjugation energies. This formal inconsistency can be explained in terms of the solvation effect.
Breitlinien 185Re- und 187Re-Festkörper-NMR-Spektroskopie an Metaperrhenaten mit alkylsubstituierten Kationen der V. Hauptgruppe / Wideline 185Re and 187Re Solid-State NMR Spectroscopy of Metaperrhenates with Alkyl-Substituted Cations of Main Group V
Authors: Burkert Paul K. , Grommelt Meinhard , Pietraß Tanja , Lachmann Joachim , Müller Gerhard
Published: March 2015

127I solid-state NMR spectra of metaperiodates with alkyl- or aryl-substituted cations of main group V yield second order quadrupole effects due to the distortion of the tetrahedra surrounding the iodine nuclei. In some cases the 127I quadrupole effects were found to become very small or even vanish. Thus the isomorphous metaperrhenates should also be accessible by 185Re, 187Re solid-state NMR. Owing to the very large quadrupole moments of the 185Re and 187Re isotopes, very small distortions or changes in dynamical effects can be detected in systems with such voluminous cations.

The solid-state NMR spectra of (CH3)4AsReO4 yield the calculated 185Re, 187Re second order quadrupole effects. These result from two kinds of differently distorted ReO4- tetrahedra. X-ray investigations and calculations based on a point charge model for (CH3)4SbReO4 manifest the inaccessibility of quadrupole effects by wideline solid-state NMR in a magnetic field of Bo = 4.698 Tesla.
BEDT-TTF-Salze mit quadratischen Platinaten(II) als Gegenionen: [BEDT-TTF]4[Pt(CN)4] / BEDT-TTF-Salts with Square Platinates(II) as Counter Ions: [BEDT-TTF]4[Pt(CN)4]
Authors: Gärtner Stephan , Heinen Ilsabe , Keller Heimo J. , Niebl Roland , Nuber Bernhard , Schweitzer Dieter
Published: March 2015

The compound [BEDT-TTF]4[Pt(CN)4], BEDT-TTF = Bis(4.5-ethylendithiolo)tetrathiafulvalen = C10H8S8, stoichiometry C44H32N4S32Pt, Mr = 1837.9 (g/mol), was obtained by electrocrystallization in at least three different modifications. Two of them could be identified by single crystal X-ray structure elucidation. 1 = β-modification, is isolated in black, lustrous platelets: triclinic, P 1̄, Z = 1, α = 9.7280(30) Å, b = 10.9237(27) Å, c = 16.5432(60) Å, a = 95.820(25)°, β = 98.296(26)°, γ = 115.215(24)°, V = 1547.56 A3, dc = 2.0 (g/cm3), room temperature, Rw = 0.082 for 7322 observed reflections. 2 = y-modification, is isolated in black not very regular crystals: monoclinic, C 2/c, Z = 4, a = 11.163(6) Å, b = 33.56(2) Å, c = 16.56(1) Å, β = 91.39(4)°, V = 6202.04 A3, dc = 1.97 (g/cm3), room temperature, Rw = 0.053 for 1404 observed independent reflections. Both solids contain sheets of BEDT-TTF cations separated by sheets of the counter anions. 1 contains two crystallographically independent BEDT-TTF moieties while 2 contains four independent donor units per cell. Of interest are the very different lengths of the central C=C bonds of the BEDT-TTF moieties which are assumed to reflect the charge density on these ions. In 1 these distances are 1.350(14) Å and 1.306(14) A, respectively, for the two different BEDT-TTF cations in the lattice, in 2 they are 1.372(34) A, 1.401(42) A and 1.289(54) Å respectively. The remarkable differences in these bond lengths indicate, according to published concepts, quite different charges on the different BEDT-TTF units. Two of the distances are shorter than in the neutral donor. Measurements of the specific resistance and the thermopower show that 1 is a metal with a room temperature conductivity of 10 S/cm. At around 200 K 1 becomes semiconducting. 2 turns out to be a semiconductor with a room temperature conductivity of 1—2 S/cm. Around 225 K a structural phase transition occurs. ESR measurements show an antiferromagnetic coupling between the spins in the solid. A third modification (δ) (semiconducting with a room temperature conductivity around 2 × 10-2 S/cm) was identified by ESR investigations.
Contributions to the Chemistry of Boron, 204 [1] An Unusual [2+2]-Cycloaddition Reaction of Dicobalt Octacarbonyl
Authors: Channareddy Sreelatha , Linti Gerald , Nöth Heinrich
Published: March 2015

Dicobalt octacarbonyl reacts with (9-fluorenylidene)(2,2,6,6-tetramethylpiperidino)borane (1) at ambient conditions in an unexpected [2+2]-cycloaddition to yield an oxaboretane derivative (2). The structure of 2 has been determined by X-ray diffraction analysis. Similarities between the complex 2 and other oxaboretanes are discussed.
Bestimmung von Oberflächenoxiden auf Rußen durch potentiometrische Direkttitration in nichtwäßrigen Lösungsmitteln / Determination of Surface Oxides on Carbon Blacks by Direct Potentiometric Titration in Non-Aqueous Solvents
Authors: Besenhard J. O. , Gansmann H. P. , Meyer H.
Published: March 2015

An attempt is made to quantitatively determine acidic and basic surface oxides on carbon blacks and also to monitor their acid and base strength distribution by direct potentiometric titrations in non-aqueous media.

In contrast to direct titration procedures proposed so far, our method allows to distinguish clearly between several types of acidic surface oxides of different acid strength. This is mainly achieved by improvements of the non-aqueous titration media. The total contents of weakly and strongly acidic and also of basic oxides determined by this very fast method is comparable to results obtained by slow and laborious indirect titrations.
α-Trifluormethylsubstituierte α-Hydroxysäuren mit Alkinfunktionen in der Seitenkette / α-Trifluoromethyl Substituted α-Hydroxy Acids with Alkyne Functions in the Side Chain
Authors: Sewald Norbert , Burger Klaus
Published: March 2015

Trifluoromethyl substituted α-hydroxy acids with alkyne functions in the side chain are obtained on reaction of trifluoro pyruvates with alkynyl Grignard reagents and alkali metal salts of alkynes, respectively.
Interaction between Monovalent and Multivalent Metals and Fulvic Acids A Streaming Current Detection Study
Authors: Weis Michael , Frimmel Fritz H.
Published: March 2015

The complexation reaction between metal cations of different valence states (Al, Bi(III), Cr(III), Fe(III); Ca, Co(II), Cu(II), Mn(II), Ni(II), Pb(II), Zn; Na) and fulvic acids is investigated by the streaming current detection technique. It can be shown that the metal complexation capacity does not only depend on the nature of the cation but also on the origin of fulvic acids, which were isolated from anaerobic and aerobic landfill leachates.
Erdalkaliquadratate, VII [1] Eine neue Koordinationsvariante des Quadratatdianions in BeC4O4· 3H2O / Alkaline-Earth Squarates, VII [1] A New Coordination Mode of the Squarate Dianion in BeC4O4· 3 H2O
Authors: Robl Christian , Kinkeldey Daniela
Published: March 2015

Single crystals of BeC4O4 · 3 H2O were prepared from aqueous solution. The X-ray structure determination revealed a new coordination mode of the squarate dianion. C4O4
2- is bound to Be2+ by only one of its oxygen atoms. Three water molecules join the Be coordination sphere to form a slightly distorted tetrahedron together with the Osquarate atom. Be-Osquarate bond lengths are negligibly shorter than Be—OH2 distances. Strong hydrogen bonds occur between water molecules and all Οsquarate atoms not bound to Be2+. These Osquarate atoms act as proton acceptors in two hydrogen bonds, each of almost equal strength. One intramolecular hydrogen bond occurs within the BeC4O4.3 H2O moieties which are connected to each other by intermolecular hydrogen bonds. C4O4
2- does not deviate markedly from planarity. Difference electron density maps show evidence for bent bonds in the C4 ring system of C4O4
2-.
Mehrfachbindungen zwischen Hauptgruppenelementen und Übergangsmetallen, LXXIX. / Multiple Bonds between Main Group Elements and Transition Metals, LXXIX.
Authors: Herdtweck Eberhardt , Kiprof Paul , Herrmann Wolfgang A. , Kuchler Josef G. , Degnan Ian
Published: March 2015

Trimethylstannyl perrhenate, (CH3)3SnOReO3 (2), synthesized from dirheniumheptoxide and tetramethyltin, has a zigzag-chain crystal structure. This structure originates from catenation of individual molecules via the tin atom to a perrhenate group of another molecule. The tin atom thus forms the center of a trigonal-bipyramidal coordination geometry, with two oxygen atoms adopting apical positions while three methyl groups define the equatorial plane. The Re—O—Sn bonds alternate between linear and slightly bent. The zigzag-aggregation of the chain-structure results from the tetrahedral [ReO4] subunits. Ionic contributions to the Re—O—Sn bonds are not evident from the structural data, nor do data obtained from solution indicate any ionization such as [(CH3)3Sn]+[ReO4]⁻. Following the synthesis of the title compound 2, the heavier congener triphenylplumbyl perrhenate (5) has been synthesized from Re2O7 and Pb(C6H5)4.
Synthese und elektronenmikroskopische Untersuchung kontrolliert gewachsener, ligandstabilisierter Goldkolloide sowie theoretische Überlegungen zur Oberflächenbelegung durch Kolloide / Synthesis and Electron Microscopic Investigation of Controlled Grown, Ligand Stabilized Gold Colloids and Theoretical Considerations on the Covering of Surfaces by Colloids
Authors: Schmid Günter , Lehnert Andreas , Kreibig Ulrich , Adamczyk Zbignew , Belouschek Peter
Published: March 2015

18 nm Gold colloids are used as seeds for a controlled growth of 36 nm colloids which are then stabilized by P(m-C6H4SO3Na)3. These colloids can be isolated as golden leaflets and are readily soluble in water in virtually any concentration. Electron microscopic investigations prove a very small particle size distribution. X-ray powder diffraction and molecular weight determinations support the results of the electron microscopic investigations. The distance between the colloidal particles in two-dimensional layers corresponds to double-layers of phosphane ligands around each colloid, twice 1.2 nm. Isolated colloids seem to possess thicker ligand shells. A single 44 nm colloid shows a corona of about 7.2 nm thickness, corresponding to 12 phosphane layers. A quantitative description of two-dimensional packing densities is suggested using a novel theoretical model. By means of Monte Carlo simulations the two-dimensional structures are formed during the covering of supports of different geometry can be calculated.
Synthese und Eigenschaften cyclopropanierter 2,2′-Binaphthyldichinone / Synthesis and Properties of Cyclopropanated 2,2′-Binaphthoquinones
Authors: Laatsch Hartmut
Published: March 2015

Cyclopropanated binaphthoquinones are obtained by addition of diazomethane to dimeric naphthoquinones and thermal or acidic degradation. 8,8′-dimethoxy-3′-methyl-2,3-dihydro-2,3-methano-2,2′-binaphthyldiquinone (9b) forms diastereomers by axial chirality and has a rotation barrier of about 20 kcal/mol.
Heterocyclische Siebenring-Verbindungen, XXXV / Heterocyclic Seven-Membered Ring Compounds, XXXV
Authors: Hofmann Hans , Göttfert Christine , Gaube Helmut
Published: March 2015

Thermodynamic Data, Heterocyclic Seven-Membered Ring Compounds

On heating in carbon tetrachloride or nitromethane the 5-methoxy-1-benzothiepines 1-4 isomerize to the corresponding thionaphtholes 5-8, whereas in cyclohexane from 1-4 the usual desulfuration products C arise. Kinetic and thermodynamic data have been estimated for the reactions 3 → 7 and 4 → 8. If the thermal rearrangement of 3 resp. 4 takes place in presence of cyclohexene sulphide, one gets the desulfuration products C also in carbon tetrachloride or nitromethane as solvent together with the equimolar amount of cyclohexene. This behaviour leads to the assumption of a S2-spezies as the primary elimination product of sulphur from the episulphide intermediate A.
Boron Spirochelates Derived from Some Hydroxamic Acids and Carboxylic Acids
Authors: Das M. K. , Chakraborty S.
Published: March 2015

A number of boron spirochelates of the general formula B[R′CON(R)O]Y have been synthesized by the single-pot reaction of boric acid, a hydroxamic acid R′CON(R)OH and a carboxylic acid H2Y. The spirochelates have been characterized by elemental analyses, by IR, NMR (1H and 11B) and UV spectra and conductance measurements. They are non-electrolytes.
Beiträge zur Chemie des Phosphors, 204. Zur Existenz eines Triphosphacyclobutenid-Ions P3CH2
Ɵ / Contributions to the Chemistry of Phosphorus, 204. On the Existence of a Triphosphacyclobutenide Ion P3CH2
e
Authors: Baudler Marianne , Hahn Josef
Published: March 2015

The structure of the reaction product of white phosphorus and sodium in diglyme which exhibits a low field AB2 system in the 31P{1H} NMR spectrum [4] has been reexamined. According to the results of a complete analysis of its proton coupled 31P NMR spectrum (ABB′XX′ system), the compound is the hitherto unknown 1,2,3-triphosphacyclopentadienide ion P3(CH)2
⊖ (4), and not the triphosphacyclobutenide ion P3CH2
⊖(3) previously assumed [4]. The parameters of the Ρ,Η-coupled 31P NMR spectrum of the tetraphosphacyclopentadienide ion P4CH⊖ (2) have also been calculated.
The Molecular Structures of Hexamethyldistannane, (CH3)6Sn2, and Dimethylditellurane, (CH3)2Te2, by Gas Electron Diffraction
Authors: Haaland Arne , Hammel Andreas , Thomassen Hanne , Volden Hans V. , Singh Harkesh B. , Khanna Pawan K.
Published: March 2015

Gas electron diffraction data of (CH3)6Sn2 and (CH3)2Te2 are consistent with molecular models of D3 and C2 symmetry and bond distances Sn–Sn = 277.6(3) pm and Te–Te = 268.6(3) pm, respectively.
Reaktionen von unsymmetrischen λ5P – λ3P-Diphosphorverbindungen und von Diphosphinen (λ3P – λ3P) mit o-Chinonen / Reactions of Unsymmetrical λ5Ρ – λ3Ρ Diphosphorus Compounds and of Diphosphines (λ3P – λ3P) with o-Quinones
Authors: Breker Johannes , Schmutzler Reinhard , Dorbath Bernd , Wieber Markus
Published: March 2015

The reaction of λ5Ρ – λ3Ρ diphosphorus compounds with o-quinones, e.g. tetrachloro-o-benzoquinone or 2,5-di-tert-butyl-o-benzoquinone, led not only to oxidative addition of the o-quinone to λ3Ρ but also to insertion of a further molecule of o-quinone into the P–P bond (i.e. λ5Ρ – λ3Ρ diphosphorus compound and o-quinone reacted in a molar ratio 1:2). In the course of these oxidative addition and insertion reactions the o-quinones were converted into the corresponding hydroquinones (i.e. catechols). The products of these reactions were characterized by NMR and mass spectrometric methods, and by elemental analysis. The hydrolysis of the 1:2 addition products proceeded with cleavage of a P–O–C (hydroquinone) bond and formation of mononuclear products, involving λ4Ρ and λ5Ρ, respectively. A mechanism of this hydrolysis is proposed and has been elucidated by independent synthesis of some products. Diphosphines, i.e. symmetrical λ3Ρ – λ3Ρ diphosphorus compounds, were found to react with o-quinones in the same fashion in a molar ratio 1:3, i.e. with oxidative addition of the o-quinone to both λ3P atoms and insertion of tetrachloro-o-catechol into the P–P bond.
Synthese und Kristallstruktur von [Hg2(p-SC6H4NO2)]NO3 / Synthesis and Crystal Structure of [Hg2(p-SC6H4NO2)]NO3
Authors: Brodersen Klaus , Knörr Axel
Published: March 2015

[Hg2(p-SC6H4NO2)]NO3 is formed by the reaction of p-nitrothiophenol with dimercury(I)-dinitrate in methanol. It crystallizes in the monoclinic space group P21/n with a = 1175.5(9) pm, b = 1079.8(8) pm, c = 876.2(8) pm, β = 110.74(4)° and Z = 4. The crystal structure has been determined by X-ray diffraction and refined to an R-value of 0.052. The results show that the compound exists as a chain structure of

[—®S(C6H4NO2)— Hg— Hg—]n with nitrate ions connecting the chains.
Elektronentransfer und Ionenpaare, 15 [ 1– 3] Radikalanion und Radikal-Kontakt-Ionenpaare von Dimesityl-tetraketon / Electron Transfer and Ion Pairing, 15 [1-3] Radical Anion and Radical Ion Pairs of Dimesityl Tetraketone
Authors: Bock H. , Hänel P. , Herrmann H.-F.
Published: March 2015

The radical anion of dimesityltetraketone (ERed, I = -0.40 V) is easily generated in THF by potassium mirror/[2.2.2]-cryptand reduction. Its contact ion pairs with Na⊕, Cs⊕ and Ba⊕⊕ counter cations, prepared in THF solution by single electron transfer from the respective metals, are characterized by their ESR/ENDOR spectra, which exhibit temperature-dependent metal couplings of aNa
⊕ = 0.061 mT (190 K), aCs
⊕ = 0.021 mT (190 K), and aBa
⊕⊕ = 0.145 mT (295 K).