bluuebunny/crossref_metadata_2025 huggingface dataset:
Chemical Composition of an Unusual Xenolith of the Allende Meteorite
Authors: Palme H. , Kurat G. , Spettel B. , Burghele A.
Published: February 2015

The chemical composition of an unusual xenolith (All-AF) from the Allende meteorite was determined by neutron activation and x-ray fluorescence analyses. The xenolith is similar in bulk composition to Allende, but has large excesses in some moderately volatile trace elements, such as Na, K, Au, Sb etc. Some of these elements show considerable variations in other components of Allende, suggesting inhomogeneous distribution in Allende. However, elements of higher volatility, such as Zn and Se have concentrations typical of bulk Allende and other type 3 carbonaceous chondrites. Therefore, All-AF must have formed from the same reservoir as bulk Allende.

All-AF has uniform grain size and does not, and did never, contain chondrules. The low content of volatile elements, therefore cannot be ascribed to loss of volatiles during the chondrule forming process. It is a characteristic of the Allende reservoir. The chemical composition of related dark inclusions (DIs) in Allende is different from All-AF. Dark inclusions may have formed by separation of fine grained material in the early solar nebula while All-AF resembles bulk Allende material that was never subject to chondrule formation. Both, dark inclusions and All-AF have oxygen isotopic compositions which plot at the upper end of the δ18O vs. δ17O correlation, suggesting extensive oxygen exchange with ambient gas.
Evidence of Chaotic Hierarchy in a Semiconductor Experiment
Authors: Parisi J. , Peinke J. , Huebener R. P.
Published: February 2015

We study the cooperative spatio-temporal behavior of semiconductor breakdown via both probabilistic and dynamical characterization methods (fractal dimensions, entropies, Lyapunov exponents, and the corresponding scaling functions). Agreement between the results obtained from the different numerical concepts (e.g., verification of the Kaplan-Yorke conjecture and the Newhouse- Ruelle-Takens theorem) gives a self-consistent picture of the physical situation investigated. As a consequence, the affirmed chaotic hierarchy of generalized horseshoe-type strange attractors may be ascribed to weak nonlinear coupling between competing localized oscillation centers intrinsic to the present semiconductor system
Liquid Crystalline Norcholesterylesters: Influence of the Axial Methylgroups on the Phase Transitions and the Cholesteric Helix
Authors: Stegemeyer H. , Siemensmeyer K. , Sucrow W. , Appel L.
Published: February 2015

Liquid crystalline norcholesteryl anisic esters were prepared in which the methylgroups 19, 21, 27, and 18 are removed successively from the cholestene skeleton. The influence of the axial methylgroups on the phase transition temperatures and the choleric helical structure has been investigated. On heating the 18.19.21.27-tetranorcholesteryl ester, at 155 °C an inversion of the helical screw sense from left to right was observed
Resonance Transition of the Spatial Correlation Factor of Self-Generated Oscillations in the Postbreakdown Regime of p-Ge
Authors: Schöll E. , Naber H. , Parisi J. , Röhricht B. , Peinke J. , Uba S.
Published: February 2015

The linear correlation factor of spatially coupled nonlinear self-generated oscillations in the post-breakdown regime of p-Gc at 4.2 K is investigated. The observed results can be consistently explained in terms of a two-cell model of energy relaxation oscillations, which yields resonance transitions between correlated and anticorrelated oscillations. These are due to node-focus transitions of the fixed point of the passive cell which is slaved by the active cell.
The Microwave Spectrum and Nuclear Quadrupole Coupling Constants of HNC17O
Authors: Gerry M. C. L , Howard S. J. , Heineking N. , Dreizler H.
Published: February 2015

The microwave spectrum of HNC17O is reported for the first time. The measurements were made with both Stark modulated and microwave Fourier transform spectrometers. The 17O and 14N quadrupole hyperfine structure has been resolved and rotational, centrifugal distortion and 17O and 14N quadrupole coupling constants have been evaluated. The 17O coupling constants are compared with those from an ab initio prediction.
Atomic Structure of Amorphous Fe-Tb-and Amorphous Fe-Co-Tb-Alloys by Means of EDXD
Authors: Utz R. , Brunsch A. , Lamparter P. , Steeb S.
Published: February 2015

We present structural investigations using the energy dispersive X-ray diffraction (EDXD)- method on amorphous Fe-Tb- and Fe-Co-Tb-alloys over an extended concentration range. Atomicdistances. partial coordination numbers, and chemical short range order parameters are reported. The short range order is characterized by a compound forming tendency. In an amorphous Fe-Co- Tb-alloy, doping with hydrogen affects the short range order and gives rise to an in-plane magnetization direction.
Studies on Molecular Motionsand Phase Transition in Pyridinium Tetrachloroiodate(III)Crystals by the Measurements of the Temperature Dependences of Chlorine Nuclear Quadrupole. Resonance Frequencies and Relaxation Times
Authors: Ishikawa Atsushi , Asaji Tetsuo , Nakamura Daiyu
Published: February 2015

To elucidate the phase transition of pyridinium tetrachloroiodate(III) at Tc = 217 K, the temperature dependences of the chlorine NQR frequencies and corresponding NQR spin-lattice and spin-spin relaxation times (T1Q and T2Q) have been measured in the range 77-370 K. Above ca. 370 K and between 206 and 223 K no chlorine NQR frequency could be observed, the chlorine relaxation times becoming extremely short (ca. 100 μs). Except for near Tc, the T1Q values below ca. 310 K can be explained by fluctuations of the electric field gradient at the chlorine nuclei due to in-plane reorientations of the cations about their pseudohexad axis. The increase of T1q
-1 in the vicinity of Tc suggests a critical slowing down of the orientational fluctuations of the cations and a distortion of the complex anions. The decrease of T1Q above 310 K is considered to be mainly due to the in-plane reorientation of the complex anions. An activation energy of 64 kJ mol-1 is evaluated for that motion.
3.5-Di-tert-butylstyrole: Synthese sterisch anspruchsvoller Polymerbausteine / 3.5-Di-tert-butylstyrenes: Synthesis of Bulky Polymer Building Blocks
Authors: Risch Nikolaus , Meyer-Roscher Bernd , Langhals Maria
Published: February 2015

We report the synthesis of 3,5-di-tert-butylstyrene (5). The alkylation of toluene with tertbutylchloride establishes the 1,3,5-substitution pattern. A Wittig reaction introduces the C1 unit. This and similar bulky styrene derivatives will be used as special building blocks for polymer design.
Synthese und Struktur von l,2-Bis(organozinn-boryl)ethen-Derivaten / Synthesis and Structure of l,2-Bis(organotin-boryl)ethene Derivatives
Authors: Frankhauser P. , Pritzkow H. , Siebert W.
Published: February 2015

Trimethyltinlithium reacts with z-1,2-bis(diisopropylamino-chloro-boryl)ethene derivatives 4a (R = Et) and 4b (R = H) to give the cis-1,2-bis(diisopropylamino-trimethyltin-boryl)- hexene-3 (2a) and, surprisingly, the trans-1,2-bis(diisopropylamino-trimethyltin-boryl)- ethene (5 b) respectively. The constitution of 2 a and 5 b is derived from spectroscopic data, and confirmed by X-ray structure analyses. The formation of the trans-product 5 b probably occurs via a radial intermediate.
Kristallstruktur des „supramolekularen“ Quecksilber(II)chlorid-thiocyanat- Hexamethylentetramin-Addukts Hg(SCN)2 · 2HgCl2 · 2C6H12N4 / Crystal Structure of the “Supramolecular” Mercury(II) Chloride Thiocyanate Hexam ethylenetetram ine Adduct Hg(SCN)2 · 2HgCl2 · 2C6H12N4
Authors: Pickardt Joachim , Gong Gill-Taik , Röleke Dietmar
Published: February 2015

Crystals of the adduct Hg(SCN)2 · 2HgCl2·2C6H12N4 were obtained from an aqueous solution containing 0.1 mol/l hexamethylenetetramine and 0.05 mol/l potassium thiocyanate and mercury(II) chloride. The compound crystallizes monoclinically; space group P21/n, a = 767.3(4), b = 1854.7(7), c = 872.5(7) pm, and β = 101.48(5)°. The structure consists of a net­ work of chains -Cl-Hg-Cl-Hg- and -(Cl-Hg-)2NCS-Hg-SCN-(Hg-Cl)2-which share common Hg atoms and form distorted hexagonal and trigonal channels. The hexamethylenetetramine molecules lie in the hexagonal channels. They act as μ3 bridging ligands, forming bonds to two Hg atoms in a given layer, and an additional bond to a Hg atom a neighbouring layer.
Metallkomplexe mit biologisch wichtigen Liganden, LXXII [1]. Halbsandwichkomplexe von Iridium(III) und Ruthenium(II) mit Dianionen von 2-Hydroxyiminocarbonsäuren / Metal Complexes of Biologically Important Ligands, LXXII [1]. Half Sandwich Iridium(III) and Ruthenium(II) Complexes with Dianions of 2-Hydroxyiminocarboxylic Acids
Authors: Bergs Ralph , Lampeka Rostislav , Robl Christian , Beck Wolfgang
Published: February 2015

Chiral chelate complexes with dianions of 2-hydroxyiminocarboxylic acids

(1) und

(2) are obtained by deprotonation of the compounds

and

in the presence of a donor ligand (Do=PR3, P(OMe)3, py). The structure of

has been determined by X-ray diffraction.
Sr3[Al2N4]: Ein Nitridoaluminat mit gewellten Tetraederketten 1
∞[AlN4/2
3–] / Sr3[Al2N4]: A Nitridoaluminate with Corrugated Tetrahedral Chains 1
∞[AlN4/2
3-]
Authors: Blase Wolfgang , Cordier Gerhard , Ludwig Matthias , Kniep Rüdiger
Published: February 2015

Sr3[Al2N4] (Pnna, Nr. 52; a = 590.1(3), b = 1000.5(5), c = 958.0(4) pm; Z = 4) was prepared from the elements (molar ratio Sr: Al = 3:1; reaction with N2, 1 atm, 24 h; Tmax = 1100 °C). The crystal structure contains corrugated chains 1
∞ [AlN4/2
3-] which consist of distorted AlN4 tetrahedra sharing common edges (Al-N : 188.5(7)-195.8(7) pm; N-Al-N : 95.0(3)- 126.0(5)°). The nitrogen atom s form a distorted ccp arrangement. 3/4 of the octahedral holes are occupied by Sr atoms; 1/4 of the tetrahedral holes are occupied by Al atoms. Sr3[Al2N4] can be described in terms of the Zintl concept (isosteric relation of [AIN2]3- to SiS2).
Metallkomplexe mit funktionalisierten Schwefelliganden, VIII [1]. 4-Phenyl-1,2-dithiolan-1-oxid, ein stabiles, fünfgliedriges cyclisches Thiosulfinat / Metal Complexes of Funetionalized Sulfur Containing Ligands, VIII [1]. 4-Phenyl-1,2-dithiolane-1-oxide, a Stable, Five-Membered Cyclic Thiosulfinate
Authors: Weigand Wolfgang , Bosl Gabriele , Dielingen Bernd von , Gollnick Klaus
Published: February 2015

Sensitized photooxidation of 4-phenyl-1,2-dithiolane 1 has been studied. Reacting it with 0.5 mole equivalents o f singlet oxygen, a mixture of 1, 4-phenyl-1,2-dithiolane-1-oxide 2, and 4-phenyl-1,2-dithiolane-2-dioxide 3 is produced. Using one mole equivalent of singlet oxygen, 3 is obtained in high yields. The chemical oxidation of 1 using H2O2/HOAc yields pure 2. With 2 a diastereoselectivity of 10:1 is observed. The oxidative addition of 1 to L2Pt(η2-C2H4)[L=PPh3 (4), 1/2 dppe (5)] leads to the 3-phenyl-propane dithiolato complexes

6a,b. The platinum(O) com pound 4 reacts with 2 to give the bimetallic compound

7 and the monometallic species

. These complexes contain the 3-sulfido-l-(2-phenyl)-propanesulfenato ligand. All com pounds have been characterized by their spec­ troscopic data.
Elektronentransfer und Ionenpaar-Bildung, 33 [1, 2]. Die Einelektronen-Reduktion von Tetraphenyl-p-benzochinon mit Alkalimetallen: ENDOR-Spektren von Kontaktionen-Paaren sowie Tripelionen in Lösung und Einkristallstrukturen der Neutralverbindung und ihres Natrium-Salzes / Electron Transfer and Ion Pair Formation, 33 [1,2]. The Single Electron Reduction of Tetraphenyl-p-benzoquinone by Alkali Metals: ENDOR Spectra of Contact Ion Pairs as well as Triple Ions in Solution and Single Crystal Structures of Both the Neutral Compound and its Sodium Salt
Authors: Bock Hans , John Andreas , Kleine Markus , Näther Christian , Bats Jan W.
Published: February 2015

Tetraphenyl-p-benzoquinone, according to its single crystal structure, shows some steric congestion: its quinone ring is distorted by 7° to a chair conformation, and its phenyl substituents are twisted around their CC axes between 46° and 72°. The half-wave reduction potentials of -0.57 and -1.25 V in acetonitrile confirm negligible π interaction of the phenyl substituents. Addition of alkalimetal tetraphenylborate salts lowers the second reduction potential due to contact ion formation, which can be confirmed by UV/VIS spectra recorded under aprotic conditions. Extensive ESR/ENDOR investigations prove the formation of the following species in THF solution: Tetraphenyl-p-benzosemiquinone radical anion contact ion pairs [M·⊖ Me⊕
solv]' (Me⊕: Li⊕, Na⊕, Rb⊕, Cs⊕) and contact triple ion radical cations both with identical cations [M·⊖ (Me⊕
solv)2]·⊕ (Me⊕: Li⊕, Na⊕, Cs⊕) and different cations [M·⊖ (Li⊕
solv)(Me⊕
solv)]·⊕ (Me⊕: Na⊕, Cs⊕). Addition of crown ethers can lead to external solvation of the Me⊕ counter cations, whereas cryptands form internal solvation complexes. The radical anion of 2,6-diphenyl-p-benzosemiquinone adds cations at its phenyl-free molecular half. The radical anion salt [tetraphenyl-p-benzosemiquinone·⊖ (Na⊕(tetrahydropyrane) 2)] could be crystallized and its structure determined at 200 K. In agreement with the Hirota sign rules for contact radicals in solution, the Na⊕ ion is found 62 pm above the π plane and 29° outside the axis of the CO bound, which is elongated due to one-electron reduction by 5 pm to 127 pm.
Gold(I) Complexes of Organic Nitrogen Compounds: Synthesis and Structures of (Phthalimido)(triphenylphosphine)gold(I) in Crystals C6H4(CO)2N(AuPPh3) and C6H4(CO)2N( AuPPh3) · CHCl3
Authors: Lange Peter , Schier Annette , Riede Jürgen , Schmidbaur Hubert
Published: February 2015

[O(AuPPh3)3]+BF4
- has been found to be a powerful aurating reagent for phthalimide, to give (phthalimido)(triphenylphosphine)gold(I) (1) in high yield. Two different crystal sys­tems, with or without CHC13 molecules in the unit cell, have been obtained. In both cases the monoaurated diacylamido complex C6H4(CO)2N(AuPPh3) (1) is present as a monomer with linear two-coordinate gold atoms. The N-Au(I) bond lengths (2.028(4), 2.040(4) Å) are similar to those found in other monoaurated complexes of the type R]R2N(AuPPh3) with strongly electron-withdrawing organic substituents R1, R2. Crystal data: 1, monoclinic, P21/c, a = 9.948(1), b = 15.712(1), c = 14.651(1) Å, β = 103.40(1)°, V = 2227.7 Å3, Z = 4; 1·CHCl3, orthorhombic, P212121, a = 8.889(1), b = 10.349(1), c = 29.198(2) Å, V = 2686.0 Å3, Z = 4.
Die Kristallstrukturen von Li[PF6] und Li[AsF6]: Zur Kristallchemie von Verbindungen A[EVF6] / The Crystal Structures of Li[PF6] and Li[AsF6]: On the Crystal Chemistry of Compounds A[EVF6]
Authors: Röhr Caroline , Kniep Rüdiger
Published: February 2015

Li[PF6] (rhombohedral, R3̅; a = 493.2(2), c = 1265.8(4) pm; Z = 3) and Li[AsF6] (rhom­bohedral, R3̅; a = 501.6(1), c = 1302.8(4) pm; Z = 3) are isotypes of the Li[BiF6] structure. The Ev-elements P(As) as well as lithium are in a nearly perfect octahedral coordination by fluorine.

The crystal structures of the fluoro-compounds A[EVF6] (A = Li, Na, K, Rb, Cs; Ev = P, As, Sb, Bi) can be divided in two groups: i. with A and Ev in a NaCl like arrangement and ii. with A and Ev in a CsCl like arrangement. The coordination numbers (CN) of the A-sites (CN between 6 and 12) depend on the ratio of radii r(EV5+)/r(A+).
Übergangsmetallkomplexe mit Schwefelliganden, CI*. Synthese und Struktur von N2H5[Fe(N2H4)(S2C6H4)2] · 1,33N2H4 / Transition Metal Complexes with Sulfur Ligands, Cl*. Synthesis and Structure of N2H5[Fe(N2H4)(S2C6H4)2] · 1,33N2H4
Authors: Sellmann Dieter , Friedrich Helge , Knoch Falk
Published: February 2015

Attempts to coordinate N2H4 to [Fe(S2C6H4)2] fragments lead to N2H5[Fe(N2H4)(S2C6H4)2], which crystallizes from MeOH/N2H4 solutions as the solvate [(N2H5){Fe(N2H4)(S2C6H4)2} · 1,33 N2H4]. 1, and has been characterized by X-ray structure analysis. 1 contains three discrete N2H5
+ cations, four N2H4 solvate molecules and three independent [Fe(N2H4)(S2C6H4)2]- anions which are connected via an extended network of N-H ··· N and N-H ··· S bridges. N2H5[Fe(N2H4)(S2ChH4)2] and 1 contain high-spin Fe(III) centers and labile N2H4 ligands.
Tris(1,10-phenanthroIine)iron(II) Complexes. Influence of 4,7-Donor Substitution on the Redox Potential [1]
Authors: Levis Michael , Lüning Ulrich , Müller Michael , Schmittel Michael , Wöhrle Clemens
Published: February 2015

Several new 4.7-donor substituted 1.10-phenanthrolines were synthesized and the corre­sponding tris(1,10-phenanthroline)iron(II) complexes were studied by cyclic voltammetry. All iron(II) complexes showed fully reversible waves at scan rates between 50 and 500 mV/s. For some redox systems the kinetics in their reaction with chlorine was studied. Complexes 7k and 71 significantly extent the potential range of tris(1,10-phenanthroline)iron(II) complexes.
Synthesis of Novel 3-Acetyl-2-hydroxy-1-N,N-diacetylaminocarbazole Derivatives
Authors: Sekar M. , Vanitha S. , Prasad K. J. Rajendra
Published: February 2015

The synthesis of hitherto unknown 3-acetyl-2-hydroxy-1-N,N-diacetylaminocarbazole (3a-f), is reported. The hydroxyiminocarbazoles (2a-f), prepared from 1-oxo-1,2,3,4-tetra-hydrocarbazoles (1a -f) on treatment with acetyl chloride in acetic anhydride yielded the title compounds (3a-f).
Uber die Darstellung von (CH3)2SSSH+SbF6
-und (CH3)2SSSCH3
+SbCl6
-[1] / On the preparation of (CH3)2SSSH+SbF6
- and (CH3)2SSSCH3
+SbCl6
-[1]
Authors: Minkwitz Rolf , Kornath Andreas
Published: February 2015

The preparation of the thiosulfonium salts (CH3)2SSSH+SbF6
- and (CH3)2SSSCH3
+SbCl6
- from (CH3)2SSCl+SbF6
- and (CH3)2SSH+SbCl6
-, resp., at 195 K is reported. (CH3)2SSSH+SbF6
- is transformed into (CH3)2SSSCl+SbF6
- by reaction with Cl2 at low temperatures. The salts have been characterized by their Raman spectra
Zur Struktur und Dotierung von Selenosilikaten: die Kristallstruktur von Er2SeSiO4 und Er3,75Ca0,25Se2,75Cl0,25Si2O7 Structure and Doping of Seleno Silicates: the Crystal Structures of Er2SeSiO4 and Er3,75Ca0,25Se2,75Cl0,25Si2O7
Authors: Stöwe Klaus
Published: February 2015

Well-shaped brown and pink isometric crystals were obtained as by-products of the synthesis of erbium selenides from the elements in evacuated and sealed silica ampoules with graphite inlets. They could be identified as erbium seleno mono- and disilicates by energy dispersive X-ray fluorescence and X-ray structure determination. The monosilicate Er2SeSiO4 crystallizes isotypically to Nd2SeSiO4 in the space group Pbcm with the lattice parameters a = 600.2(2), b = 688.0(2), c = 1075.2(2) pm and represents the second known seleno inosilicate of the rare earths. From X-ray structure analysis an isotypic relation between the disilicate Er3,75Ca0,25Se2,75Cl0,25Si2O7 and the compound Sm4S3Si2O7 was found, the former crystallizing in the space group I41/amd with the lattice parameters a - 1177.7(2) and c = 1376.5(2) pm. The doping o f the sorosilicate with the elements Ca and Cl originated from contam inations in the graphit inlets used in the procedure
U3TiSb5, U3VSb5, U3CrSb5, and U3MnSb5 with "Anti"-Hf5Sn3Cu Type Structure
Authors: Brylak Markus , Jeitschko Wolfgang
Published: February 2015

The title compounds have been prepared from the elemental components by arc-melting and subsequent annealing. Single crystals of U3TiSb5 and U3MnSb5 were obtained from a tin flux and their structures were determined from single-crystal X-ray data: P63/mcm, Z = 2; a = 913.9(2), c = 611.2(1) pm, R = 0.011 (233 structure factors, 14 variables) for U3TiSb5 and a = 916.8(2), c = 613.2(1) pm, R = 0.015 (427 structure factors, 14 variables) for U3MnSb5. The lattice constants of the isotypic compounds are: a = 908.2(2), c = 608.3(2) pm for U3VSb5 and a = 911.0(1), c = 611.5(1) pm for U3CrSb5. The structure of these antimonides may be regarded as an “anti”-type structure of Hf5Sn3Cu with the antimony atoms on the hafnium sites, while the positions of the uranium and transition metal atoms correspond to the positions of the tin and copper atoms. A comparison of the interatomic distances of U3TiSb5 with those of U3Sb4, USb2, and a-antimony suggests oxidation numbers according to (U+III)3Ti+IV(Sb1-III)3(Sb2-II)2, where the Sb2 atoms form weakly bonded chains
Organophosphorverbindungen mit tertiären Alkylsubstituenten. III*: Synthese und Reaktionen Di-1-adamantylsubstituierter Phosphorverbindungen; Kristallstruktur von Di-1-Adamantylphosphinsäurechlorid / Organophosphorus Compounds with Tertiary Alkyl Substituents. Ill: Synthesis and Reactions of Di-1-adam antyl-Substituted Phosphorus Compounds; Crystal Structure of Di-1-adam antylphosphinic Chloride
Authors: Goerlich Jens R. , Fischer Axel , Jones Peter G. , Schmutzler Reinhard
Published: February 2015

The reaction of adamantane with PCl3/A1Cl3, followed by hydrolysis, gave (1-Ad)2P(:O)Cl 1, which was converted to (1-Ad)2P(:O)F 2 and (1-Ad)2P(:S)Cl 3 by standard procedures. The structure of 1 was confirmed by a single crystal X-ray structure determination; despite the bulky substituents the P-C bond lengths are normal (184.0(3), 185.0(3) pm). Whereas chlorine-fluorine exchange in 3 with AsF3 furnished (1-Ad)2P(:S)F 4, desulfuration of 3 with Ph3P to give (1-Ad)2PCl 5 failed. The secondary phosphine oxides R 1R2P(:O)H (R1, R2 = 1-Ad: 6; R1 = 1-Ad, R2 = tBu: 7; R1, R2 = tBu: 8) were synthesized by reaction of 1, 1-AdP(:O)Cl2 and tBuP(:0)Cl2 with tBuLi. 6 and 8 reacted readily with chloral to give the adducts R2P(:O)CH(OH)CCl3 (R = 1-Ad: 9; R = tBu: 10). Silylation of 6 with Me2NSiMe3 in the presence of dry air led to (1-Ad)2P(:O)OSiMe3 11, which was hydrolyzed to give (1-Ad)2P(:O)OH 12. (1-Ad)2POSiMe3 13 was obtained by the reaction of 6 with n-BuLi, followed by Me3SiCl. No reaction took place upon heating 6 with Mo(CO)6. (1-Ad)2PCl 5 was synthesized in low yield by the reaction of 6 with PCl3. The action of tetrachloro-obenzoquinone (TOB) upon 6 furnished (1-Ad)2P(:O)(o-OH)C6Cl4 15, whereas the tbutyl analogue of 15, 16, was synthesized by hydrolysis of the TOB-adduct of di-tbutylfluorophosphine. Analogous 1-adamantyl- and tbutyl-phosphorus compounds are compared with regard to their 31P NMR data
Tris [(trimethylsilyl)oxy] antimony
Authors: Baier Michael , Angermaier Klaus , Schmidbaur Hubert
Published: February 2015

Tris[(trimethylsilyl)oxy]antimony (Sb(OSiMe3)3, 1) has been prepared from SbCl3 and 3 equiv. of LiOSiMe3 in diethylether. According to mass spectrometric and NMR spectroscopic data, 1 appears to be a monomer in solution and in the gas phase. Dimerisation occurs, however, in the solid state as verified by an X-ray crystal structure determination. The unit cell contains three crystallographically independent monomers, two of which form one type of dimer, while the other is part of a centrosymmetrical dimer. In both types of dimers two Sb atoms are connected via two OSiMe3 groups to form distorted Sb2O2-squares. Together with the remaining 4 OSiMe3 groups and the two stereochemically active lone pairs, each Sb exhibits a trigonal bipyramidal coordination.
Ein cyclisches Organoantimon(III)-oxid, (RSbO)4 [R = (Me3Si)2CH] / A Cyclic Organoantim ny(III) Oxide, (RSbO)4 [R = (Me3Si)2CH]
Authors: Breunig Hans Joachim , Mohammed Mohammed A. , E b ert Klaus H.
Published: February 2015

The cyclic organostibane oxide [(Me3Si)2CHSbO]4 (1) has been prepared by reaction of RSbCl2 with KOH in water/diethylether and crystallization as 1·H2O from petroleum ether. The crystal structure of 1·H2O consists of a boat shaped 8-membered Sb4O4 heterocycle with the substituents in trans positions (distances Sb-O 197.0(3) pm, Sb-C 217.2(4) pm, angles O-Sb-O 93.2(1)°, Sb-O-Sb 122.3(2)°, O-Sb-C 96.2(1)°) and disordered water molecules. Crystal data: tetragonal, space group 14̅; a = 16.091(2), c = 11.057(2) Å; Z = 2.
Kristallstrukturen der [2.2.2]Cryptate [Cd(cryptand 222)][CdCl4] und [Hg(cryptand 222)][Hg2Cl6] mit achtfach koordinierten Metallionen / Crystal Structures of the [2.2.2]Cryptates [Cd(cryptand 222)][CdCl4] and [Hg(cryptand 222)][Hg2Cl6] with 8-Coordinated Metal Ions
Authors: Pickardt Joachim , Kühn Britta
Published: February 2015

Reactions of [2.2.2]cryptand, 4,7,13,16,21,24-Hexaoxa-1,10-diazabicyclo-[8.8.8]hexacosane, (“cryptand 222”) with cadmium chloride and mercuric chloride yielded crystals of [Cd(cryptand 222)][CdCl4] (1) and [Hg(cryptand 222)][Hg2Cl6] (2). 1 crystallizes tetragonally, space group P42/n, Z = 4, a = 1239.8(2), c = 1801.2(8) pm; 2 is monoclinic, space group P2/n, Z = 2, a = 1060.3(3), b = 955.2(2), c = 1607.0(3) pm. and β = 108.85(2)°. In the cations of both complexes the metal ions are enclosed in the bicyclic ligand and show 8-coordination to its six oxygen and two nitrogen atoms, the coordination polyhedron is a distorted cube for 1 and a bicapped trigonal antiprism for 2. The anion of 2 is dimeric, the two mercury atoms are connected via chlorine bridges with Hg-Cl distances of 258 and 278 pm, the Hg-Cl bond lengths to the two terminal chloro ligands being shorter at 236 and 238 pm.
1,2-Di(silyl)benzene and 1,4-Dibromo-2,5-di(silyl)benzene
Authors: Schröck Robert , Sladek Alexander , Schmidbaur Hubert
Published: February 2015

1,2-Di(silyl)benzene (3), has been prepared in a three-step process starting with the reac­tion of 1,2-dibromobenzene and p-tolyl(chloro)silane with magnesium in tetrahydrofuran. which affords 1,2-bis(p-tolylsilyl)benzene (1) as a stable high-yield intermediate. Compound 1 has been converted into 1,2-bis(trifluoromethanesulfonatosilyl)benzene (2) with trifluoro- methanesulfonic acid, and finally into 3 by reduction with lithiumaluminiumhydride, both again in high yields. - In an attempt to prepare 1,2,4,5-tetra(silyl)benzene in an analogous way. only the bis-silylated species could be obtained (from 1,2,4,5-C6H2Br4. p-MeC6H4SiClH2 and Mg powder: 1,4-dibromo-2,5-bis(p-tolylsilyl)benzene. 4, and 1,4-dibromo-2,5-di(silyl)- benzene, 6, via 1,4-dibromo-2,5-bis(trifluoromethanesulfonatosilyl)benzene, 5). The crystal structures of compounds 4 and 6 have been determined by X-ray diffraction. The results indicate no steric hindrance in these molecules and it is thus not obvious from the molecular structures why the silylation reaction does not proceed any further to give the tetrasilylated benzene derivatives. Electronic effects have to be invoked to rationalize the experimental findings.
MgNi2P - das erste ternäre Phosphid mit geordneter Fe3C-Struktur / MgNi2P - The First Ternary Phosphide with an Ordered Fe3C Type Structure
Authors: Keimes Viktor , Mewis Albrecht
Published: February 2015

MgNi2P was prepared by heating a mixture of the elements and investigated by means of single crystal X-ray methods. The compound crystallizes in an ordered Fe3C-type structure (Pnma; a = 6.477(1) Å, b = 6.364(1) Å, c = 5.001(1) Å; Z = 4). Ni and P atoms are linked together to a three-dimensional framework with octogonal tubes running along [010], which are occupied by Mg atoms in the form of stretched zigzag chains.
Darstellung, 11B-, 13C-, 1H-NMR- und Schwingungsspektren von 1.2-Trimethylenpentahydro-closo-Hexaborat(1 - ) , cis - [B6H5(CH2)3]- und 1.2-Tetramethylenpentahydro-closo-Hexaborat(1-), cis-[B6H5(CH2)4]- sowie Kristallstrukturen von [P(C6H5)4][B6H5(CH2)3] und [P(C6H5)4][B6H5(CH2)4] / Preparation, 11B, 13C, 1H NMR and Vibrational Spectra of 1.2-Trim ethylenepentahydro-closo-hexaborate(1-), cis-[B6H5(CH2)3]-, and 1.2-Tetramethylenepentahydro-closo-hexaborate(1-), cis-[B6H5(CH2)4]-, and the Crystal Structures of [P(C6H5)4][B6H5(CH2)3] and [P(C6H5)4][B6H5(CH2)4]
Authors: Lübbe W. , Franken A. , Preetz W.
Published: February 2015

By reaction of [B6H6]2- with diiodopropane or diiodobutane in dichloromethane the 1,2- rimethylene-pentahydro-closo-hexaborate(1-), cis-[B6H5(CH2)3]-, and the 1,2-tetra-methylene- entahydro-closo-hexaborate(1-), dv-[B6H5(CH2)4]- are obtained, respectively. The compounds were separated from excess [B6H6]2- by ion exchange chromatography on diethylaminoethyl cellulose. The crystal structures of [P(C6H5)4][B6H5(CH2)3] (I) and [P(C6H5)4][B6H3(CH2)4] (II) have been determined by single crystal X-ray diffraction analy­sis: I is triclinic, space group P1̅ with a = 7,388(2), b = 12,254(2), c = 14,415(2) Å, α = 85,638(12)°, β= 84,06(2)°, γ = 85,13(2)°; II is monoclinic, space group P21/c with a =9,7855(10), b = 11,0793(10), c = 25,2386(10) Å, β= 2,491(10)°. The 11B NMR spectra of oth compounds reveal the feature of a cis-disubstituted octahedral B6 cage. The 13C NMR pectrum of I exhibits a quartet at 15,46 ppm with 1J(C,B) = 121,7 Hz (B-CH2) and a triplet at 37,98 ppm with 1J(C,H) = 124,4 Hz (CH2). For II a quartet at 12,89 ppm with 1J(C,B) = 105,5 Hz (B-CH2) and a triplet at 30,00 ppm with 1J(C,H) = 124,4 Hz (CH2) are observed. In the 1H NMR spectrum of I two multiplets at 0,73 and 1,90 ppm of the CH2 groups and two singlets at 2,23 and -3,71 ppm of the BH fragments are bserved; the signals of the CH2 groups of II are at 0,60 and 1,35 ppm and of the BH fragments at 2,15 and -4,81pm,respectively. The IR and Raman spectra exhibit five very strong CH stretching bands between 2807 and 2938 cm-1 in case of I and between 2817 and 2889 cm 1 in case of II.
Oxo- und Non-oxovanadium(IY)-Komplexe mit Oxy-Carboxylaten als Liganden, und die Struktur von VCl2(salen) / Oxo and Non-oxovanadium(IV) Complexes with Oxy-Carboxylate Ligands, and the Structure of VCl2(salen)
Authors: Vergopoulos Vassilios , Jantzen Sven , Julien Nathalie , Rose Eric , Rehder Dieter
Published: February 2015

V02+ forms complexes of composition VO(L1)EtOH), VO(HL1)2 and VO(HL2)(H2O) with the ithium or sodium salts of 6-droxymethyl-pyridine-2-arboxylic acid (H2L1) and 4,8-hydroxyquinoline-2-carboxylic acid (H3L2). VCl2(salen/salphen) and VCl2(napgly/ nappa) (napgly and nappa are the Schiff bases derived from o-ydroxynaphthaldehyde and glycine or phenylalanine, respectively), prepared from the oxo precursor and SOCl2, react with Li2L1 and the lithium salts of benzilic acid (H2L3) and ortho-ydroxybenzoic acid (H2L4) to yield the non-oxo (“bare”) complexes V(salen)L1 , V(salen)L3, V(salphen)L3, V(salen)L4, V(napgly)L1, V(nappa)L1, and V(nappa)L4. The complexes have been characterized by IR, EPR and elemental analyses. VOCl2(salen) crystallizes in the monoclinic space group Cc, a = 14.579(3), b = 9.537(2), c = 13.453(3) Å, β=120.92(3)°. The molecule exhibits gross distor­tions from octahedral geometry. An improved synthesis for H2L1 is described.
Em neues Alkalimetall-Kupfer-Oxovanadat: KCu5V3O13 / On a New Alkaline Copper Oxovanadate KCu5V3O13
Authors: Martin F.-D. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of KCU5V3O13 were prepared by recrystallization from flux. The black crystals show triclinic symmetry, space group Ci
1-P1̅, a = 6.0858, b = 8.2605, c = 10.6937 Å, α = 97.815, β = 92.317, γ = 90.477°, Z = 2. KCu5V3O13 is strongly related to KMgCu4V3O13, showing VO4 tetrahedra, trigonal bipyramids and stretched square pyramids around Cu2+. K+ is surrounded by ten oxygen. The crystal structure is discussed with respect to other magnesium containing copper vanadium oxides.
Synthese und Kristallstruktur von Cu0.25Ho1.25W2O8 / Synthesis and Crystal Structure of Cu0.25Ho1.25W2O8
Authors: Szillat Holger , Müller-Buschbaum Hanskarl
Published: February 2015

Single crystals of Cu0.25Ho1.25W2O8 were prepared by recrystallization from melts and investigated by X-ray diffractometer technique. Cu0.25Ho1.25W2O8 crystallizes with mono­clinic symmetry, space group C2/c, a = 19.123, b = 5.613, c = 11.479 Å, β = 111.44°. Z = 8. It represents a new structure type characterized by W4O18 groups and Cu+/Ho3+ at one point position in statistical distribution. Cu+/Ho3+ show an octahedral coordination. Another point position is occupied by Ho3+ with C. N. = 7.
Ring-Opening of (-)-Camphorsulfonimide Derivatives and (+)-Fenchonesulfonimide by Nitronium Tetrafluoroborate
Authors: Wagner Gabriele , Verfürth Uwe , Herrmann Rudolf , Krüger Carl
Published: February 2015

Treating a derivative of (-)-camphorsulfonimide (CA name: (3aS)-8,8-dimethyl-4,5,6,7- tetrahydro-3H-3a.6-methano-2,1-benzisothiazole 2,2-dioxide) or the isomeric (+)-fenchonesulfonimide with nitronium tetrafluoroborate in acetonitrile does not lead to the expected products of cationic reactions, e.g. of the Ritter reaction for halogenated compounds, but provokes a cleavage of the sulfonimide group with the formation of a ring-opened product containing a sulfonyl fluoride and a nitroimine group. The reaction does occur only in the presence of solid nitronium tetrafluoroborate. but not after prior dissolution of the reagent. An X-ray structure of the product from (1 S)-3-endo-bromocamphorsulfonimide confirms this unusual reaction.
Fünffach koordinierte Komplexe vom Typ [tripodM-(ortho-(X)(Y)C6H4)]n (X, Y = O, S) bei d5-, d6- und d7-systemen. synthese, struktur, elektrochemie und esr-spektren / Five-coordinate complexes [tripodM-(ortho-(X)(Y)C6H4)]n (X, Y = O, S) with d5-,d6- and d7-Systems. Synthesis, Structure, Electrochemistry and ESR-Spectra
Authors: Körner Volkmar , Asam Alexander , Hüttner Gottfried , Zsolnai Laszlo , Büchner Michael
Published: February 2015

The d6-Co(III)-species [tripodCo-(ortho-(X)(Y)C6H4)]+ (X, Y = O, S, tripod = CH3C(CH2PPh2)3) 1 are reversibly reduced to the neutral d7-Co(II)-compounds [tripodCo-(ortho-(X)(Y)C6H4)] (X, Y = O, S) 2. Both species show fivefold coordination of cobalt with coordination polyhedra in between the limits of the square pyramid and the trigonal bipyramid respectively. The low-spin d7-species 2 give clearly resolved ESR-spectra revealing the coexistence of two geometric isomers above -80 °C, with only one isomer persistent at temperatures around 100 K.

As an analogous d5-system [benzyltripodFe-(ortho-(S)(S)C6H4)]+ 3 (benzyltripod = C6H5CH2C(CH2PPh2)3) has been obtained from [benzyltripodFe(NCCH3)3]2+ and C6H6S2. Alternatively complexes of this type, e.g. [tripodFe-(ortho-(S)(S)C6H4)]+ 4, may be prepared from Fe(H2O)6(BF4)2/tripod/C6H6S2 when the reaction mixture is activated by acidification with HBF4. The geometry of the d5-species 3 and 4 is close to a trigonal bipyramid
Haemophaein, ein Dibenzofuran aus der Flechte Phyllopsora haemophaea / Haemophaein, a Dibenzofuran from the Lichen Phyllopsora haemophaea
Authors: Himmelreich Uwe , Huneck Siegfried
Published: February 2015

Haemophaein, a metabolite of the lichen Phyllopsora haemophaea has been structurally elucidated as 1-(2',2'-dihydroxyheptyl)-3,6-dihydroxy-8-(2"-oxoheptyl)-dibenzofuran-2- carboxylic acid-9,2'-lactone
Borylation of 1,1′-Dibromoferrocene and Alkylferrocenes
Authors: Wrackmeyer Bernd , Dörfler Udo , Rinck Joachim , Herberhold Max
Published: February 2015

1,1′-Dibromoferrocene (1) and alkylferrocenes (ethylferrocene 2a, n-butyiferrocene 2b) react stepwise with an excess of boron tribromide in hexane to give first the monoborylated ferrocenes (3, 5a, 6a) followed by the diborylated ferrocenes (4, 7a, 8a). In the case of 4, two diastereomers are obtained. The triborylated ferrocene derivatives 9a,b are obtained in high yield as the final products. The proposed structures of all borylated ferrocenes are supported by a consistent set of 1H, 13C and 11B NMR data.
Factors Influencing the Acid Lability of Substituted Arylsulphonyl Arginine Protecting Groups
Authors: Ali Syed Safdar , Echner Hartmut , Khan Khalid Mohammed , Schröder Christoph , Hasan Mashooda , Atta-ur-Rahman  , Voelter Wolfgang
Published: February 2015

The kinetics of hydrolysis of new, NG-protected 2,4,6-triisopropylbenzene-sulphonyl (6). 4-methoxy-3,5-di-tert-butylbenzenesulphonyl (12) and phenanthrene-3-sulphonyl (17) Fmoc derivatives of L-arginine (1) in comparison with commercially available Fmoc-Arg(Mtr)-OH (Mtr = 4-methoxy-2,3,6-trimethyl-benzenesulphonyl (2)) are studies. The acid lability of the arylsulphonyl group is decreasing as follows Mtr > Tip > Mtbs > Phen. The effect of electron- donating alkyl groups as substituents in increasing the acid lability of the arylsulphonyl residue seems to be in the order of methyl > isopropyl > tert-butyl while the effect of extended derealization does not appreciably increase the acid lability.
Ein Beitrag zur Kristallchemie von Verbindungen mit Johillerit-Struktur: KCo3Cu(As2,58V0,42)O12 / On the Crystal Chemistry of Compounds with Johillerite Structure: KCo3Cu(As2,58V0,42)O12
Authors: Frerichs D. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of KCo3Cu(As2.58V0.42)O12 were prepared by solid state reactions below the melting point of the reaction mixture (K2CO3, CuO, COC2O4, V2O5 and 3 As2O5 · 5H2O). It crystallizes with monoclinic symmetry, space group C6
2h-C2/c, a = 12.207, b = 12.730, c = 6.811 Å, β = 113.69°, Z = 4. The structure type is characterized by isolated twisted-square CuO4-polygons, CoO6-octahedra and a special 4+4-coordination of the potassium ion. As5+ and V5+ are in tetrahedral coordination with a partly statistical distribution of these ions.
Zur Reaktion von Carben-Addukten des Kohlenstoffdisulfids mit Brom und Iod [1] / On the Reaction of Carbene Adducts of Carbon Disulfide with Bromine and Iodine [1]
Authors: Kuhn Norbert , Bohnen Hans , Henkel Gerald
Published: February 2015

The carbene adducts 3 are obtained as stable solids from the imidazol-2-ylidenes 1 and CS2. 3 c reacts with bromine to give the cationic bromosulfane 4, whereas iodine forms the charge-transfer adduct 5. Oxidative coupling to the dicationic disulfane 6 is observed with excess of iodine. The X-ray structure analyses of 3b, 4, 5 and 6 are reported.
Wasserlösliche Phosphane, III [1]. Wasserlösliche primäre Phosphane mit Ammoniumgruppierungen NR2R' in der Seitenkette -donorfunktionalisierte Amphiphile / Water-Soluble Phosphanes, III [1]. Water-Soluble Primary Phosphanes with Ammonium Groups NR2R' in the Side Chain -Donor-Functionalized Amphiphiles
Authors: Brauer David J. , Fischer Jörg , Kucken Stefan , Langhans Klaus P. , Stelzer Othmar , Weferling Norbert
Published: February 2015

Primary and secondary aminoalkylphosphanes R2N-(CH2)m-PH2 (R2 = Me2, nBu2, C5H10, C4H8O, 2-(1-Methyl-2-pyrrolidinyl); m = 2, 3, 6, 10, 11; 1-6) or [R2N-(CH2)m]2PH (7, R2 = C5H10; m = 2) are accessible by aminoalkylation of PH3 with ω̃ -chloroalkylamines R2N-(CH2)m-Cl in the superbasic medium DMSO/KOH (DMSO = dimethylsulfoxide). By selective N-quaternization of 1, 2, 4-6 with R'I (R' = Me, CnH2n+1; n = 6-8, 12, 16, 18) in the two-phase system CH2Cl2/H2O novel primary phosphanes [R'R2N-(CH2)m-PH2]+I- (11-16f) with quaternary ammonium groups in the alkyl side chain are obtained. The water solubility of 11-16f decreases with increasing chain length (n) of R′ 11 (R = R' = Me; m = 2) shows a trans conformation at the C2H4 bridge according to an X-ray structural analysis. Protonation of 1, 2, 4, 5 with HCl affords the water-soluble hydrochlorides [HR2N-(CH2)m-PH2]+Cl- (19-22). The cationic primary phosphanes 11-16f are stable towards oxygen. By oxidation of 11 with one or two equivalents of H2O2 the primary phosphane oxide [Me3N-(CH2)2-P(O)H2]+I- (23) or the phosphonous acid [Me3N-(CH2)2- P(O)(OH)H]+I- (23a) are formed. Hofmann degradation of 11 or 16c with KOH yields phosphirane in good yields. Reaction of 1, 2, 4-6 (L) with Fe2(CO)9 at ambient temperature yields stable complexes (CO)4FeL (26-30). Under more rigorous conditions Fe3 clusters (31, 32) with free R2N groups are obtained.
Zur Reaktion von Natriumtetracarbonylcobaltat mit Aluminiumtrichlorid. Molekiilstruktur von Co4(CO)13Al(THF)3Co3(CO)10 / On the Reaction of Sodium Tetracarbonylcobaltate with Aluminiumtrichlorid. Molecular Structure of Co4(CO)13Al(THF)3Co3(CO)10
Authors: Schneider Jörg J. , Denninger U. , Krüger C.
Published: February 2015

The reaction of NaCo(CO)4 with AlCl3 in benzene has been studied. Main product of the reaction is Co4(CO)12. However, fractional crystallization of the crude reaction mixture gives small amounts of black crystals of the cobalt cluster Co4(CO)13Al(THF)3Co3(CO)10

A single crystal structure determination has revealed a quasi-octahedrally coordinated Al atom which is bridging a Co3(CO)9-oxymethylidin-tricobalt-nonacarbonyl cluster unit and a Co4-carbonyl cluster unit. Three THF ligands are completing the octahedral environment of the group-III metal. The aluminium atom is bonded to the oxygen atoms of three μ3-bridging CO groups of the Co3- and Co4-cluster fragments.
Metallkomplexe mit biologisch wichtigen Liganden, LXXIV [1]. Metallorganische Verbindungen von 2-(3-Thienyl)glycin und dessen Derivaten / Metal Complexes with Biologically Important Ligands, LXXIV [1]. Organometallic Compounds of 2-(3-Thienyl)glycine and Derivatives thereof
Authors: Schuhmann Elfriede , Robl Christian , Beck Wolfgang
Published: February 2015

N.O-Chelate complexes of R,S-2-(3-thienyl)glycinate (L) have been obtained: ML2 (M = Ni, Cu), (n-Bu3P)(Cl)M(L) (M = Pd. Pt), (η3-C3H5)Pd(L), C6H4CH,CHNMe2Pd(L), (η6-p-cymene)(Cl)Ru(L), (η5-C5Me5)(Cl)M(L) (M = Rh, Ir) and (η5-C5H5)(OC)2Mo(L). The methyl ester of R,S-2-(3-thienvl)glycine (L') forms the complexes trans-CT2PdL′2, cis- Cl2Pt(L')2, (η-Bu3P)(Cl2)M(L') (M = Pd, Pt) and (η5-C5Me5)(Cl)2M(L') (M = Rh, Ir) in which the ligand L' is coordinated through the amino group. The structures of (η3-C3H5)Pd(L) and of (η5-C5Me5)(Cl2)Ir(L') have been determined by X-ray diffraction. N- Benzoyl-2-(3-thienylglycine methyl ester reacts with Cr(CO)6 to yield a tricarbonyl complex with an η6-coordinated phenyl group. N-Benzoyl-R,S-2-(3-thienyl)glycinate (L") and (η5- C5H5)2TiCl2 give the diastereoisomers [(η5-C5H5)2Ti(R-L")(R-L")2/(η5-C5H5)2Ti(S-L") (S-L")] and (η5-C5H5)2Ti(R-L")(S-L") with Ti-O-bonds.
Die Darstellung sterisch anspruchsvoller Phosphinoester und ihre Verwendung zur Synthese von Rhodium(I)-und Rhodium(III)-Komplexen [1] / The Preparation of Sterically Demanding Phosphinoesters and their Use for the Synthesis of Rhodium(I) and Rhodium (III) Complexes
Authors: Wolfsberger Werner , Burkart Wolfgang , Bauer Sonja , Hampp Andreas , Wolf Justin , Werner Helmut
Published: February 2015

Two routes for the preparation of sterically demanding phosphinoesters RR′P(CH2)nCO2Me (n=1,2 or 3) and RR′P(CH2)nCO2Et (n=1 or 2) have been developed: (1) reaction of trimethyl-silyl phosphines RR′PSiMe3 (R=R′=/Pr. rBu) with ω-chloroalkylesters, and (2) hydrophos- phination of secondary phosphines HP(R)Ph (R = Me, Et. Pr. iPr, iBu) with unsaturated carboxylic esters. From iPr2PCH2CO2Me (3) and iPr2PCH2CO2Et (4), a variety of rhodium(I) and rhodium(III) complexes, mainly with alkyne and vinylidene ligands, have been prepared. Compound [RhCl(C8H14)2]2 (19) reacts with four equiv. of 3 to give [RhCl(iPr2PCH2CO2Me)2] (20) which on further treatment with CO affords the carbonyl complex trans-[RhCl(CO)(iPr′>PCH2CO2Me)2] (21). The related ethylene derivative trans-[RhCl(C2H4)(iPr2PCH2CO2Me)2] (23) is obtained from [RhCl(C2H4)2]2 (22) and 3. Compound 20 reacts with H2 and HCl by oxidative addition to yield [RhHXCl(iPr2PCH2CO2Me)2] (24, 25) and with RC≡CR′ to give the alkyne complexes trans-[RhCl(RC≡CR′)(iPr2PCH2CO2Me)2] (26-28). The analogous compounds trans- RhCl(HC≡CR)(iPr2PCH2CO2Me)2] (29, 30), equally prepared from 20 and HC≡CR, both rearrange thermally and photochemically to produce the vinylidene isomers trans-[RhCl(=C=CHR)(iPr2PCH2CO2Me)2] (31, 32). In contrast, propyne reacts with 20 to give the allene complex trans-[RhCl(CH2=C=CH2)(iPr2PCH2CO2Me)2] (33). The synthesis of [RhCl(iPr2PCH2CO2Et)2] (34) and the corresponding alkyne and vinylidene adducts 35 and 36, obtained with HC≡CCO2Me as the substrate, is also described.
Synthese benzoverbrückter, fünfgliedriger ES2C2-Heterocyclen mit ECl-Baueinheiten (E = P, As, Sb, Bi) ausgehend von 1.2.4.5-Tetramercaptobenzol / Synthesis of Benzo-Bridged, Five-Membered ES2C2 Heterocycles with ECl Moieties (E = P, As, Sb, Bi) Starting from 1,2,4,5-Tetramercaptobenzene
Authors: Köpf Hartmut , Balz Hellfried
Published: February 2015

The benzo-bridged, heterocyclic compounds [E(Cl)S2-1,2]C6H2[4,5-S2E(Cl)] (E = P (1), As (2), Sb (3), Bi (4)) have been obtained as air-stable solids from the reaction of ECl3 with 1.2.4.5-(HS)4C6H2 in diethyl ether. 1-4 are insoluble in common solvents and have been characterized mainly by elemental analyses and their infrared and mass spectra.
Ubergangsmetall-substituierte Acylphosphane und Phosphaalkene, XXIY [1]. Dipolare [3+2]- und [2+2]-Cycloadditionen von Carbonyl-aktivierten Alkinen an (η5-C5Me5)(CO)2Fe-P=C(NMe2)2. Synthese und Struktur des 1-Phospha-1,3-butadiens (η5-C5Me5)(CO)2Fe-P=C(E)-C(E)=C(NMe2)2(E=CO2Me) / Transition Metal Substituted Acylphosphanes and Phosphaalkenes, XXIV [1]. Dipolar [3+2]- and [2+2]-Cycloadditions of Carbonyl Activated Alkynes to (η5-C5Me5)(CO)2Fe-P=C(NMe2)2. Synthesis and Structure of the 1-Phospha-1,3-butadiene (η5-C5Me5)(CO)2Fe-P=C(E)-C(E)=C(NMe2)2(E=CO2Me)
Authors: Weber Lothar , Kaminski Olaf , Stammler Hans-Georg , Neumann Beate , Boese Roland
Published: February 2015

The metallophosphaalkene (η5-C5Me5)(CO)2Fe-P=C(NMe2)2 (1) was converted into the stable metallated 1-phospha-1,3-butadiene, (η5-C5Me5)(CO)2Fe-P=C(E)-=C(NMe2)2 5a) and the [3+2]-cycloadduct

(4a) by treatment with the alkyne E-C≡C-E (E=CÒ2Me). A similar reaction of 1 with Me-C≡C-E (E = CQ2Me) resulted in the formation of the 1,2-dihydrophosphete

(6). The cycloadduct

(4c) was the sole tractable product from the reaction of 1 with the alkyne Ph-C≡C-C(0)tBu. The compounds 4a-c, 5 a, b and 6 have been characterized by elemental analysis as well as by spectroscopic data (IR, 1H, 13C, 31P NMR, MS). The molecular structures of 4a, 5a and 6 have been determined by single crystal X-ray analysis.
Elektrophile Aktivierung von OH-Gruppen in Phosphor-organischen Verbindungen - Eine Anwendung für Phosphan-Borane / Electrophilic Activation of OH Groups in Organophosphorus Compounds - An Application of Phosphane Boranes
Authors: Seitz Th. , Hüttner G. , Büchner M.
Published: February 2015

In the synthesis of oligophosphane ligands containing the neopentyl framework, the electrophilic activation of an OH group in com pounds of the type R′CH2C(CH2OH)(CH2PR2)2 is a serious problem which may be overcome by BH3 protection of the intrinsically nucleophilic phosphane groups. It is shown that the hydroxy group of HOCH2C(CH2PPh2)3 (1) may be mesylated to yield MsOCH2C(CH2PPh2BH3)3 (3) after protection of 1 as its BH3 derivative (2).
Bromierung von „Poly(1,4-diselenobenzol)“ / Bromination of “Poly(1,4-diselenobenzene)”
Authors: Jung Annette , Wolmershäuser Gotthelf
Published: February 2015

“Poly(1,4-diselenobenzene)”, obtained by reaction of 1,4-dibromobenzene with disodiumdiselenide is shown to contain many different polymer sequences. Bromination of the polymer yields a variety of low molecular weight species thus confirming the non-uniformity of the polymer and giving some hints about its composition. The aryl-selenium-bromine compounds 1,4-benzene-diselenenyldibromide, 4,4′-di(bromoselenenyl)-diphenylseleniumdibromide, and bromo-bis(4-bromophenyl)selenonium hexachloroantimonate were fully characterised inclu­ding X-ray structure determinations.
Diphenyl(1-pyridyl)phosphine Sulfide as a Ligand in Mono-and Binuclear Coinage Metal Complexes
Authors: Olmos M. Elena , Schier Annette , Schmidbaur Hubert
Published: February 2015

Diphenyl(1-pyridyl)phosphine sulfide, Ph2pyPS, 1, gives a 1:1 complex (2) with AuCl upon treatment with (C4H8S)AuCl. According to an X -ray diffraction analysis, this compound is isomorphous with the Ph3PS complex. [Ph3PAu]BF4 and 1 give the cationic complex [Ph3PAuSPpyPh2]BF4 (3 ) . With two equivalents of the same reagent the binuclear complex 4 is generated, in which the metal atoms are S- and N-bonded. The reaction of 2 equivalents of 1 with [(tetrahydrothiophene)2Au]ClO4 affords the 2:1 complex 5 with the gold atom exclusively S-bonded. The analogous reaction with AgBF4 gives the 2:1 complex 6, the structure of which has also been determined by X-ray diffraction. The silver atom is engaged in coordinative bonding with both sulfur and both nitrogen atoms in a quasi-tetrahedral environment. Addition of AgClO4 to com pound 5, and of [(MeCN)4Cu]B F4 to 6, gives mixed-metal complexes (7, 8) with head-to-head structures, the silver atoms being exclusively S-bonded.