bluuebunny/crossref_metadata_2025 huggingface dataset:
Dibenzoylmethane Reaction with Dichlorophenylphosphine: Oxygen Transfer from Carbon to Phosphorus via a Defined C2PO3 Phosphorane
Authors: Dahlhoff Wilhelm V. , Taba Kalulu M. , Mynott Richard
Published: March 2015

Abstract Dichlorophenylphosphine reacts with two equivalents of dibenzoylmethane at -30 °C in the presence of triethylamine to give a tricyclic phosphorane intermediate 4 which isomerizes to the more stable phosphinic acid ester 5 above 30 °C. The structures of 4 and 5 were determined by 13C, 1H shift correlated 2D NMR spectroscopy using long range couplings.
Borylierung von Sulfamiden, Sulfoniminen und Sulfondiiminen/Borylation of Sulfamides, Sulfonimines and Sulfonediimines
Authors: Einholz Wolfgang , Frey Gerhard , Haubold Wolfgang
Published: March 2015

Abstract The diborylated sulfamide 6a can be obtained from 2-chloro-1,3-dimethyl-1,3,2-diazaborolidine and the silylated sulfamide la , whereas (Me2N)2BCl and 1a yield the dithia-tetrazadiborocine 7b. Similarly, (Me2N)2BCl reacts with a) the sulfonimine 2a, b) the sulfonediimine 3a to give a) B(NMe2)3, and the bis-and tris(sulfonimino)boranes 10b and 11, b) B(NMe2)3 and the dithiatetrazadiborocine 15b. The diborylated sulfamide 6c (R2B = Ph2B) cannot be isolated. The synthesis of the monoborylated sulfonimines 9c, 9e and sulfonediimines 13, 14 is described.
Synthesis of Water Soluble Tetrairidium Clusters Suitable for Heavy Atom Labelling of Proteins
Authors: Jahn Werner
Published: March 2015

The substitution of 4 CO ligands in Ir4(CO)12 by tris-(2-carbethoxyethyl)phosphine and sub­ sequent reaction with ammonia yielded water soluble Ir clusters which when modified further can be used for heavy atom labelling of proteins.
Synthese und Kristallstruktur von [Na-15-Krone-5][WF5(NCl)] / Synthesis and Crystal Structure of [Na-15-Crown-5][WF5(NCl)]
Authors: Görge Astrid , Dehnicke Kurt , Fenske Dieter
Published: March 2015

[Na-15-crown-5][WF5(NCl)] has been prepared as yellow crystals by the reaction of NaF with WC14(NCl) in the presence of 15-crown-5 in acetonitrile solution. The compound was characterized by its IR spectrum as well as by an X-ray structure determination. Crystal data: space group P 21/n, Z = 4 (2945 observed, independent reflexions, R = 0.035). Lattice dimensions at - 65 °C: a = 827.2(8); b = 1617.3(13); c = 1372.2(10) pm; β = 99.42(5)°. The com pound forms ion pairs, in which the sodium ion is seven-coordinated by the oxygen atoms of the crown ether m olecule, and by two fluorine ligands of the [WF5(NCl)]- unit with Na -F distances of 228.3(6) and 251.3(6) pm. The W ≡ N-Cl group of the anion is nearly linear (bond angle 176.1(5)°) with bond lengths WN = 173.3(6) and NCI = 162.2(7) pm.
Nachweis der isotopomeren closo-Hydrohexaborate 11Bn
10B6-nH6
2- , n = 0—6, durch Tieftemperatur-Raman-Spektroskopie / Detection of the Isotopomeric closo-Hydrohexaborates 11Bn
10B6-nH6
2- , n = 0—6, by Low Temperature Raman Spectroscopy
Authors: Preetz W. , Thesing J.
Published: March 2015

Abstract The low temperature Raman spectra (10 K) of Cs2B6H6 and its 11B and 10B enriched derivatives prepared for the first time show well resolved signals o f the B6-cage vibrations υ1 (A1g), υ3(Eg) and υ9(T2g) for all isotopomers 11B10B6-nH6
2 -, n = 0-6. The intensities o f the sharp peaks correlate exactly with the statistical abundance ratio. W hereas the frequency decreases by nearly equidistant steps of 7 cm-1 with increasing n values, the geometric isomers for n = 2, 3 and 4 are separated by only about 2 cm-1. The band assignments are verified by Teller-Redlich calculations.
A Convenient Preparation of Bis(phosphorothioyl) Sulfides
Authors: Min Shi , Ishihara Hideharu , Murai Toshiaki , Kato Shinzi
Published: March 2015

Abstract The reaction of piperidinium and potassium phosphorodithioates with 2-chloro-1-methyl-pyridinium salts afforded the corresponding bis(phosphorothioyl) sulfides in good yields. The similar reaction with potassium diphenylphosphorothioate gave exclusively bis(diphenylphos-phorothioyl) oxide.
Reaktive E=C(p—p)π-Systenie, XIX. F3CP=C(H)F und F3CP = C(D)F als Dienophile / Reactive E=C(p—p)π-Systems, XIX. F3CP=C(H)F and F3CP=C(D)F as Dienophiles
Authors: Althoff Ulrike , Grobe Joseph , Le Van Duc , Würthwein Ernst-Ulrich
Published: March 2015

Abstract A study of the dienophilic properties of F3CP = C(H)F (1) and F3CP = C (D)F (4) has been performed by using Me3SnP(CF3)CF2H (2) and Me3SnP(CF3)CF2D (3), respectively, as precur­ sors for the in situ generation of 1 and 4 in the presence of 2 ,3-dim ethyl-1,3-butadiene, 1,3-cyclohexadiene or 9,10-dimethylanthracene. Slow elimination of Me3SnF occurs at 55 °C yielding the cycloadducts of 1 and 4, respectively, within 5 or 7 days. Polymerization is observed as the main stabilizing reaction of 1 and 4, thus reducing the yields o f the [2+4]-cycloadducts 5 to 9 to about 20%. They are formed as mixtures o f diastereomers in the ratio a:b ≈ 90:10. In the preferred isomer a according to NMR data CF3 and F have anti positions. Since NMDO calculations yield energy barriers of about 40 kcal/mol for E/Z isomerization, and literature values for inversion barriers of trialkyl phosphanes are of the same magnitude, the formation of isomers most likely has to be explained by a nonconcerted mechanism of the [2 + 4]-cycloaddition.
Radikalionen, 81. ENDOR-spektroskopische Untersuchungen an Radikalkationen aromatischer Organoschwefel-Verbindungen / Radical Ions, 81. ENDOR Spectroscopic Investigations of Radical Cations of Aromatic Organosulfur Compounds
Authors: Bock H. , Hierholzer B. , Rittmeyer P.
Published: March 2015

Conditions for ENDOR measurem ents of organosulfur radical cations are discussed and tested. The one electron oxidation of a variety of aromatic sulfur com pounds comprising benzene-1,2-dithiole, 1,4-dithiine, thianthrene and diphenylsulfide derivatives as well as 33S isotope-marked bis(2,5-dimethoxyphenyl)disulfide is accomplished using the oxygen-free, powerful and selective AlCl3/H2CCl2 reagent. Partly with substantial structural changes, paramagnetic M⊕ species of 1,2-benzodithiete, 1,4-dithiine, thianthrene and diphenyl sulfide result. Their temperature-dependent ENDOR signal patterns provide numerous information e.g. on radical cation structure and dynamics, on the rather high sulfur spin populations or on the spin rotation interaction dominated relaxation behaviour. Accordingly, to obtain optimum ENDOR effects in organosulfur radical cations low temperature measurements are required, and especially for still undiscovered 33S ENDOR couplings, small g factor anisotropies and 33S spin densities appear to be necessary.
Note on Carbonyl Derivatives with a Chiral Phosphorylhydrazine
Authors: Dehmlow Eckehard V. , Sauerbier Christiane
Published: March 2015

Hydrazones of chiral and achiral ketones with enantiomerically pure phosphorylhydrazine 4 are prepared and analysed by 31P NMR spectroscopy and HPLC for their diastereoisomeric purity.
The Space Group of (TTM-TTF)2+(AuCl4
-)2 [TTM-TTF = Tetra(methylthio)tetra- thiofulvalene]
Authors: Jones Peter G.
Published: March 2015

The space group of the title compound is probably C2/m rather than the previously reported C2.
Selenoantimonate: Darstellung und Struktur von Na3SbSe4, K3SbSe4 und [Ba(en)4]2[Ba(en)3](SbSe4)2/ Selenoantimonates(V): Preparation and Crystal Structure of Na3SbSe4, K3SbSe4 and [Ba(en)4]2[Ba(en)3](SbSe4)2
Authors: Eisenmann Brigitte , Zagler Roland
Published: March 2015

Abstract The crystal structures of Na3SbSe4, K3SbSe4 and [Ba(en)4]2[Ba(en)3](SbSe4)2 contain isolated tetrahedral anions SbSe4
3-, which are the first examples of selenoantimonates(V). Na3SbSe4 (space group 143m , a = 750.1(2) pm, Z = 2) is an isotype of the (NH4)3SbS4-structure type; K3SbSe4 (space group R3c, a = 1137.5(4) pm, c = 1359.6(4) pm, Z = 6) forms a slightly distorted variant. In the crystal structure of [Ba(en)4]2[Ba(en)3](SbSe4)2 (space group P21, a = 965.8(4) pm, b = 1764.8(8) pm, c = 1463.2(6) pm, β = 90.8(1)°, Z = 2) the cations are in six- and eight-fold coordinations by the bidentate ligands.
Heteronukleare Mehrkernkomplexe. Darstellung und Struktur von Komplexen mit den Kationen [MII{(OH)2CoIII(en)2}3]5+, M = Ni, Zn, Mg/Polynuclear Mixed-Metal Complexes. Preparation and Structures of Complexes with the Cations [MII{(OH)2CoIII(en)2}3]5+, M = Ni, Zn, Mg
Authors: Müller Susanne , Thewalt Ulf
Published: March 2015

Reaction of [(en)2Co(H2O)2](ClO4)3 with the dichlorides of nickel, magnesium , and zinc, leads at an pH of ca. 8 to the heterometallic, isomorphous complexes [MII{(OH)2CoIII(en)2}3](ClO4)4Cl·3H2O. The central metal(2 +) cations of these complexes are surrounded octahedraily by three [(en)2Co(OH)2]+ chelate ligands. This has been confirmed by X-ray structure analyses. The cation antipodes of the racemic salts exhibit the conformations Δ (⋀ ⋀ ⋀) / ⋀ (Δ Δ Δ) .
Darstellung und Kristallstruktur von NdSe1,9/ Preparation and Crystal Structure of NdSe1,9
Authors: Urland W. , Plambeck-Fischer P. , Grupe M.
Published: March 2015

NdSe1,9 has been prepared as grey, strongly reflecting platelets by reaction of elemental neodymium with selenium in the ratio 1 :2 and subsequent chemical vapour phase transport with iodine. It crystallizes in the tetragonal space group P42/n with a = 925.36(7), c = 1679.2(3) pm and Z = 20. The structure determination results in a formulation of NdSe1,9 as Nd 20(Se(I)2)8Se(I)2⃞2Se(II)20, where the defect layer built from the Se(I)2
2- and Se(I)2- ions corresponds to the F layer in the PbFCl substructure.
Reaktion des Oxovanadium(V)-trichlorids mit tert-Butylamin und silylierten Derivaten/Reaction of Oxovanadium (V) Trichloride with tert-Butylamine and Silylated Derivatives
Authors: Preuss Fritz , Fuchslocher Edith , Leber Edith , Towae Willi
Published: March 2015

A m ino and Im inovanadium (V) C om pounds, Preparation, 5IV NM R Spectra The reaction o f V O C l3 with rm -butylam ine and silylated derivatives has been studied. 0 = V C 1 2[N'C4H 9(R)] (R = SiM e3, SiM e2NH'C4H 9), 0 = V (0 S i M e 3)2Cl and binuclear vanadium (V) com plexes with bridging oxo and nitrogen ligands have been prepared; their spec­ troscopic data ('H N M R ,51V N M R , IR) are reported. A simple route for preparing'C4H 9N =V C 13 and ['C4H 9N = V (0)C 1]" is described including com plex formation with pyridine and chloride ions.
Zur direkten Synthese von Organobromgermanen aus Methylenbromid und Germanium/Kupfer-Gemischen/Direct Synthesis of Organobromogermanes from Methylenebromide and Germanium/Copper Mixtures
Authors: Schmidbaur Hubert , Rott Johann
Published: March 2015

A lkylbrom ogerm anes, Synthesis, C V D Feeding G as, G erm anium /Copper Mixtures From the copper-catalyzed reaction o f germanium powder with dibrom om ethane at 310 °C a mixture o f alkylbrom ogermanes is obtained. The major products are CH 3G eB r3, Br3G eC H 2Br
Über Verbindungen subvalenter Hauptgruppenmetallkationen mit Dithiolaten, 3. Mitteilung [1]. Die Kristallstruktur von [As(C6H5)4]2[Pb(S2C=C(CN)2)2]/Compounds of Subvalent Main Group Metal Cations with Dithiolates, Part 3 [1] Crystal Structure of [As(C6H5)4]2[Pb(S2C=C(CN)2)2]
Authors: Hummel Hans-Ulrich , Meske Hermann
Published: March 2015

The crystal structure of [AsPh4]2[Pb(S2C=C(CN)2)2] has been determined by X-ray diffraction. In the pyramidal complex anion [Pb(S2C=C(CN)2)2]2- Pb is coordinated to the sulfur atoms of the dithiolates. The geometry is indicative for a stereochemically active lone-pair at the apex of the square pyramid.
Darstellung, Kristallstruktur und Schwingungsspektren von Cs3As7 und Cs3(NH3)As7/Syntheses, Crystal Structure and Vibrational Spectra of Cs3As7 and Cs3(NH3)As7
Authors: Somer M. , Hönle W. , Schnering H. G. von
Published: March 2015

Cs3As7, a compound with cage-like As7
3- anions, has been prepared from the elements in sealed quartz ampoules at 820 K. The ruby-red compound undergoes a first order phase transition at 640 K and is obtained as microcrystalline samples. The structure of the low-temperature α-modification is not known, but β-Cs3As7 belongs to the plastically crystalline β-Rb3P7 type of structure (F m 3̄ m , a (673 K) = 1169,2(1) pm). Cs3As7 melts under its own vapour pressure at 1061 K, and is easily soluble in liquid ammonia. From those solutions ruby red crystals of Cs3(NH3)As7 precipitate. In dynamical vacuum NH3 is evaporated in the region of 300 to 520 K, resulting in Cs3As7. Cs3(NH3)As7 crystallizes in the space group P21/a (a = 2759.0(12) pm, b = 744.1(3) pm, c = 751.5(3) pm, β = 90.16(5)°; Z = 4). The structure is closely related to the plastically crystalline β-Rb3P7 type structure (Li3Bi variant). The heptaarsanortricyclene anion is coordinated by cesium atoms, connecting the anions to a three dimensional arrangement. The anion exhibits a differentiation of As - As bond lengths typical for ionic nortricyclenes (d(basis) = 251.2 pm; d(basis-bridge) = 235.5 pm; d(bridge-bridgehead) = 240.1 pm). The distances Cs to As are in the range 372 to 401 pm. The cesium atoms are surrounded by three resp. four As atoms and the NH3 molecules. The FIR and Raman spectra are given for different temperatures as well as of an en-solution of Cs3(NH3)As7. The valence vibrations of NH3 are found at 3175 (A1) and 3320 cm-1 (E ). The fundamental vibrations of the three-membered ring of different heteronortricyclenes with P and As are compared and yield a correlation factor χ = 0.57(1) for the observed frequencies between P3 and As3. The band gaps EG are determined from the diffuse reflexion at 2.14 eV for Cs3(NH3)As7 and 2.00 eV for Cs3As7.
Strukturuntersuchungen an chiralen Schiff-Basen des 11-cis-Retinals/Structure Investigation of Chiral Schiff Bases of 11-cis-Retinal
Authors: Buß Volker , Haas Verena , Wingen Ute
Published: March 2015

CD and UV spectra of four chiral 11-cis-retinal Schiff bases obtained by condensing the aldehyde with asymmetric amines are used to gain structural information about the polyene conformation. The spectra are temperature-dependent indicating the same 12-s-cis/trans equilibrium as in 11-cis-retinal. In addition, CD absorptions arise at lower temperatures whose only origin is the inherent dissymmetric nature of the retinylidene Chromophore. CNDO /S-calculations performed on the basis of force-field optimized geometries give results which can partially be rationalized on the basis of experimental data. Quantitative agreement is obtained in the case of chiral hydrogen-bonded dimers.
Die absolute Konfiguration der Juglomycine/The Absolute Configuration of the Juglomycins
Authors: Krupa Johann , Lackner Helmut , Jones Peter G. , Schmidt-Bäse Karen , Sheldrick George M.
Published: March 2015

The absolute configurations of the known juglomycins A (1) and B (2) have been elucidated by single crystal X-ray structure analysis of 1 and its 6,8-dibromo derivative (1b). The structure of 2 has been corrected; it differs from 1 in its configuration at C-4', and not at C-3' as previously assumed. Relationships with the closely related isochromanquinone antibiotics are discussed.
Notizen: Darstellung von SH3
+AsF6
- und SCl3
+SbF6
- [1]/ Preparation of SH3
+AsF6
- and SCl3
+SbF6
-[1]
Authors: Minkwitz Rolf , Gerhard Volker
Published: March 2015

The preparation and spectroscopic characterization of the sulfonium salts SH3
+AsF6
- and SD3
+SbF6
- is reported. SCl3
+SbF6
- is synthesized by chlorination of SH3
+SbFA- with Cl2 in liquid SO2.
Beiträge zur Chemie des Phosphors, 193 [1] 1,2-Bis(di-tert-butylcyclotriphosphanyl)-3,4-di-tert-butyl- cyclotetraphosphan – ein neuer P10R6-Strukturtyp / Contributions to the Chemistry of Phosphorus, 193 [1] 1 ,2-Bis(di-tert-butylcyclotriphosphanyl)-3,4-di-tert-butylcyclotetraphosphane – a Novel P10R6 Structure Type
Authors: Bäudler Marianne , Riese-Meyer Loert de , Wiaterek Christian
Published: March 2015

The first bis(cyclotriphosphanyl)diorganylcyclotetraphosphane [(t-BuP)2P]2(t-Bu)2P4 (1) has been obtained by reacting (t-BuP)2PSnMe3 with PCl3, in the molar ratio 3:1. and has been isolated in pure form. Compound 1 is formed as a mixture of two configurational isomers 1a and 1b, which differ in the relative arrangement of the trans-oriented tert-butyl groups at the two three-membered rings. The constitutional isomer, in which three atom , is obviously not stable for steric reasons.
Beiträge zur Chemie des Phosphors, 194 [1] Natriumpentaphosphacyclopentadienid: Darstellung aus weißem Phosphor und Natriumdihydrogenphosphid / Contributions to the Chemistry of Phosphorus, 194 [1] Sodium Pentaphosphacyclopentadienide: Preparation from White Phosphorus and Sodiumdihydrogenphosphide
Authors: Bäudler Marianne , Ouzounis Dimitrios
Published: March 2015

Sodium pentaphosphacyclopentadienide has been prepared as a pure NaP5/[18]crown-6/THFsolution by reacting white phosphorus with sodiumdihydrogenphosphide (P :NaPH2 = 5:1 to 5.6:1) in boiling tetrahydrofuran in the presence of [18]crown-6.
Von 1,5-funktionellen Trisiloxanen zu (SiO)4-, [Si(OSiN)2Si]- und [O(SiOSi)2N]-Ringen / From 1,5-Functional Trisiloxanes to (SiO)4-, [Si(OSiN)2Si]-, and [O(SiOSi)2N]-Rings
Authors: Schmidt-Bäse Dieter , Klingebiel Uwe
Published: March 2015

Compounds of the general formula (CMe3)2Si(R)OH, (R = Cl, OH, NH2) react with n-C4H9Li or Na to give the alkali silanolates 1-5.1-5 serve as starting materials in the reactions with chlorosilanes for the synthesis of siloxanes (6-12). Ring closure reactions of dilithiated 9,11, and 12 occur with SiCl4 (13) and Cl2SiMe2 (15, 16). 13 contains an (SiO )4, 15 an Si(OSiN)2Si. and 16 an O(SiOSi)2N eight-membered ring. Hydrolysis of 13 leads to the formation of the hydroxy-substituted eightmembered ring 14. The crystal structures of (CMe3)2Si(OH)-O-SiMe,-O-(H2N)Si(CMe3), (11) and Me2Si[OSi(CMe3)2NH]2SiMe2 (15) are reported and discussed.
Regular Octahedral Coordination of As(III) in the Anion [As3Br12]3- Structural Correlation of the Antibonding Influence of the As 4s-Orbital in Bromoarsenates(III)
Authors: Sheldrick W. S. , Fachbereich C. Horn
Published: March 2015

The bromoarsenates(lll) [Et4N]3[As3Br12] (1). [Ph4P]2[As2Br8] (2), [(n-prop)4N]2[As2Br8] (3) and {[pipH]3[As2Br9] · [pipH]Br} (4) have been prepared and their structures established by X-ray structural analysis. The central As atom in the novel face-bridged trioctahedral species [As3Br12] displays an effectively regular octahedral coordination in one of the two independent anions in the unit cell of 1. The As-Br distances are 2.671 (1) - 2.672(2) Å with Br-A s-Br angles in the range 88.8(1)-91.2(1)°. In contrast the outer As atoms exhibit a severely distorted octahedral geometry with three short As - Br terminal bonds (2.404(2)-2.409(2) Å). The [As2Br8]2- anions in 2 and 3 are centrosymmetric with the As atoms displaying a square-pyramidal coordination. A structural correlation of opposite As-Br distances in the linear three-centre Br-As···Br interactions is presented. The sum of the bond valences in bromoarsenates(III) is a minimum for the regular octahedral geometry, reflecting, thereby, the influence of the As 4s-orbital in the antibonding 2a1g MO. An empirical expression for As-Br distances in bromoarsenates(III) is derived.
Reaktionen an komplexgebundenen Liganden, XXXIX. Reaktionen der niedrigvalenten Azido-Komplexe NEt4[CpMn(CO)2N3] und [CpFe(cdpe)N3] mit Elektrophilen und 1,3-DipolarophiIen (cdpe = cis-1,2-Bis(diphenylphosphino)ethen) / Reactions of Complex Bound Ligands, XXXIX. Reactions of the Low Valent Azido Complexes NEt4[CpMn(CO)2N3] and [CpFe(cdpe)N3] with Electrophiles and 1,3-Dipolarophiles (cdpe = cis-1,2-Bis(diphenylphosphino)ethen)
Authors: Sellmann Dieter , Licht Elke , Moll Matthias , Knoch Falk
Published: March 2015

Reactions of the low valent azido complex NEt4[CpMn(CO)2N3] (1) with electrophiles preferably give the dinitrogen complex [CpMn(CO)2N2] (2). Thus, 2 forms when 1 is reacted with NOBF4, NO2BF4 or HCl/THF. respectively. 2 forms also if 1 is reacted with the 1,3-dipolarophile CI3C-CN. The reaction of 1 with CH3I. however, gives the methylamine complex [CpMn(CO)2NH2CH3], presumably via methylazido, -nitrene and -aminyl interm ediates. Cycloadditions could be achieved with the isoelectronic [CpFe(cdpe)N3] (3); 3 yields the corresponding 2-triazolato-4,5-dialkylester complexes 4 when reacted with RO2C-C=C-CO2R(4a: R = Me; 4b: R = Et). The ethyl derivative was characterized by X-ray structure analysis.
Synthesen und Kristallstrukturen der Kronenether-Komplexe [Li3(12-Krone-4)3O2CCH3] [Cd(Se4)2], {[K(18-Krone-6)]2[Hg(Se4)2]}2 und [Na(15-Krone-5)]NO3 / Syntheses and Crystal Structures of the Crown Ether Complexes [Li3(12-Crown-4)3
3O2CCH3][Cd(Se4)2], {[K(18-Crown-6)]2[Hg(Se4)2]}2, and [Na(15-Crown-5)]NO3
Authors: Kräuter Gertrud , Weller Frank , Dehnicke Kurt
Published: March 2015

[Li3(12-crown-4)3O2CCH3][Cd(Se4)2] has been prepared by the reaction of [Li(12-crown-4)]2Se6 with Cd(C2CCH3)2 in ethanolic solution. The corresponding polyselenide complex of mercury is formed by the reaction of [K(18-crown-6)]2Se6 with Hg(O2CCH3)2 in the same solvent. Both com pounds form dark red crystals, which were characterized by single crystal X-ray structure determinations. The only product to be isolated from the reaction of Bi(NO3)3·5H2O with [Na( 15-crown-5)]2Se6 in ethanolic solution was [Na(15-crown-5)]NO3, whose structure has also been determined. [Li3(12-crown-4)3O2CCH3][Cd(Se4)2]: space group Pbca, Z = 8. 1404 observed independent reflexions. R = 0.097. Lattice dimensions (19 °C): a = 1981.5(6). b = 1400.3( 1), c = 3268.9(9) pm. The compound forms a dicationic ensemble, in which three lithium ions coordinate with the oxygen atoms of the acetate ion. In the anions the cadmium atom is coordinated tetrahedrally by four selenium atoms of two Se4
2- units.

{[K (18-crown-6)]2[Hg(Se4)2]}2: space group P 1, Z = 1. 3210 observed independent reflexions, r = 0.055. Lattice dimensions (19 °C): a = 1057.4(2). b = 1130.6(2), c = 2000.1(2) pm. α = 88.52(1)°, β = 85.86(1)°, γ = 66.22(1)°. The com pound has a complex ionic structure, in which the formula units form centrosymmetric dimers through K-O contacts between two cations. In addition there are K···Se contacts with the spiro-bicyclic anions, which - together with 6 K-O bonds within the crowns - lead to the coordination number of 8 for the remaining potassium ions.

[Na(15-crown-5)]NO3: space group P212121, Z = 4. 1211 observed independent reflexions. R = 0.052. Lattice dimensions (20 °C): a = 912.9(2). b = 989.6(1). c = 1658.3(3) pm. The compound forms ion pairs, in which the sodium atom coordinates with the five oxygen atoms oi the crown ether, as well as with two oxygen atoms of the nitrate ion with Na -O bond lengths of 240 and 247 pm.
New Cyclopentadienones from Sterically Demanding Inner Acetylenes and Dicobalt-octacarbonyl
Authors: Dehmlow Eckehard V. , Winterfeldt Andreas
Published: March 2015

Acetylenes carrying one bulky substituent can be transformed into symmetrically or asymmetrically substituted cyclopentadienones 2 or 3 when they are heated with Co2(CO)8 and carbon monoxide. Intramolecular cyclizations yielding compounds 5 are also possible.
Über intramolekulare Donator-Akzeptor-Wechselwirkungen in N,N′-Dimethylharnstoff-Derivaten des Phosphors / Intramolecular Donor-Acceptor Interactions in N,N′-Dimethylurea Derivatives of Phosphorus
Authors: Kaukorat Thomas , Schmutzler Reinhard
Published: March 2015

The reaction of

1 with N, N′-dimethyl-N, N′-bis(trimethyIsilyl)urea, 2 has furnished the compound Me2NCH2CH2N(Me)P(NMe)2C(:O), 3. Following oxidation o f phosphorus in 3 through several reagents, intramolecular donor-acceptor interactions were observed when an electronegative group was bonded to phosphorus; this group, activating the phosphorus atom, should be well polarizable in solution and should readily depart from the molecule as an anion. The unusual spirophosphoranes 8, 11 and 12 could thus be synthesized. The reaction of equimolar quantities of MeOCH2CH2OPCl2, 15 with 2 has furnished 16 which is related to 3. Reaction of 15 with excess 2 constitutes a new mode o f formation of the previously reported diphosphorus compound 17.
Synthese und Kristallstruktur des cyclischen Hydrazido-Komplexes {Fe2Cl4[(NSiMe3)(CPh)]2N2} / Synthesis and Crystal Structure of the Cyclic Hydrazido Complex {Fe2Cl4[(NSiMe3)(CPh)]2N2}
Authors: Hiller Wolfgang , Hartmann Eva , Dehnicke Kurt
Published: March 2015

The title compound has been prepared by the reaction of FeCl3 with N, N, N′-tris(trimethylsilyl) benzamidine in CH2Cl2 solution as dark red, moisture-sensitive crystals. The complex was characterized by its IR spectrum as well as by an X-ray structure determination.

Crystal data: space group P21/n, Z = 2 (1178 observed independent reflexions, R = 0.089). Lattice dimensions (20 °C): a = 1240.2(2), b = 645.7(3), c = 1779.7(3) pm, β = 91.31(2)°. The compound forms centrosymmetric molecules, in which the iron atoms are members of two fused planar

heterocycles with the NN group as the com m on edge. The NN bond length (142.5(9) pm) is very close to the NN bond length of hydrazine.
Darstellung und Charakterisierung von einigen unsymmetrischen Chlordiorganophosphanen RR′PCI / Preparation and Characterization of Some Unsymmetrical Chlorodiorganophosphines RR′PCI
Authors: Han Jung Su , Wolfsberger Werner
Published: March 2015

Some unsymmetrical chlorophosphines RR′PCI were prepared by the reaction of RPCl2 (R = CH3, C2H5, i-C3H7, C6H5) with Grignard reagents R′MgCl (R′ = c-C5H9, c-C6H11, i-C3H7) and characterized by elemental analyses and spectroscopic data (IR, 31P and 13C NMR).
Die Kristallstruktur von Ga3Cl7/ Crystal Structure of Ga3Cl7
Authors: Frank Walter , Hönle Wolfgang , Simon Arndt
Published: March 2015

Trigallium heptachloride, G a3Cl7, has been prepared from GaCl3 and Ga in sealed glass ampoules. Ga3Cl7 crystallizes in the space group Pna21 (No. 33) with a = 1181.8(1) pm; b = 889.7(1) pm; c = 1057.5(1) pm; Z = 4. The compound is isotypic with KGa2Cl7
-. The Ga2Cl7
- anion has nearly C2 symmetry (gauche conformation) with d̄ (Ga -Clbridg) = 230.3 pm, d̄ (Ga -Clterm) = 214.3 pm and and ∢ Ga -Cl -Ga = 109.0°. The Ga+ ion is coordinated by ten Cl atoms (4 + 6) with d = 346.2 pm. The coordination of Ga+ and the conformation of Ga2Cl7
- are discussed in detail together with related compounds.
Di-cyano-″propyl-arsan als Edukt für den Aufbau mehrkerniger arsanverbrückter Cobalt-Cluster/Di-cyano-″propyl-arsine as Educt for the Formation of Multinuclear Arsino-Bridged Cobalt Clusters
Authors: Lang Heinrich , Lay Uwe , Zsolnai Laszlo
Published: March 2015

(nC3H7)As(CN)2 (1) reacts with CO2(CO)8 (2) to yield the cluster 3 in which two (nC3H7)As fragments are coordinated to Co(CO)n (n = 1, 2, 3) groups. The cluster 3 has been characterized

by analytical and spectroscopic data and by an X -ray analysis.
Ammonium Hexavanadate, (NH4)2V6O16: Preparation, Crystal Structure, Infrared Spectra and High-Pressure Reactions
Authors: Range Klaus-Jürgen , Eglmeier Christiane , Waal Danita de , Heyns Anton M.
Published: March 2015

Following a re-examination of several published methods for the preparation of ammonium

hexavanadate, single crystals of (NH4)2V6O16 have been grown by a reaction of V2O5 with

NH4Cl in hot aqueous solution. They are monoclinic, space group P 21/m , with a = 7.858(2),

b = 8.412(2), c = 4.995(1) Å , β = 96.43(2)°, and Z = 1. The structure was refined to R = 0.060,

wR = 0.039 for 745 unique reflections. It comprises layers built of V2O8 double square pyramids

( V - O = 1.595- 1.988 Å) and distorted VO6 octahedra ( V - O = 1.589-2.287 Å). The infrared

bands of the NH4
+- and ND4
+- groups in (NH4)2V6O16 and its deuterated analogue can be

assigned with a fair amount of certainty at 90 K under the space group P 21/m (C2h
2). The N - D

stretching modes of isotopically diluted NH3D+-groups in (NH4)2V6O16 are in agreement with

the predicted splitting into Cs, Cs and C1(2) components. The frequencies and shapes of these

modes seem to suggest that bifurcated hydrogen bonds are formed, closely resembling the corresponding

bonds in NH4VO3. The NH4
+ ions are dynamic in character in (NH4)2V6O16 and

remain so down to temperatures of 90 K. At high temperatures in a closed high-pressure system

a redox reaction between vanadium (V ) and ammonia takes place which yields VO2 as

main product. Intermediates have been found, but up to now their com position is still unknown.
Reaktionen von Re2O7 mit Iminophosphoranen - Kristallstruktur von ( O3ReN = PPh2)2C2H4/Reactions of Re2O7 with Iminophosphoranes - Crystal Structure of (O3ReN = PPh2)2C2H4
Authors: Roesky Herbert W. , Hesse Detlev , Rietzel Mathias , Noltemeyer Mathias
Published: March 2015

Re2O7 reacts with (Me3SiN = PPh2)2CH2, (Me3SiN = PPh2)2C2H4 and Me3SiN = PPh3 to give (O3ReN = PPh2)2CH2 (3), (O3ReN = PPh2)2C2H4 (6) and Ph3P= NReO3 (7). 6 has been characterized

by X-ray crystallography. The complex crystallizes in the space group P 1̄ with unit cell dimensions a = 837.4(4), b = 873.0(5), c = 1102.5(6) pm, ɑ = 112.53(4), β = 98.54(4), γ = 100.59(4)°, and Z = 1. The structure demonstrates that the bis(diphenylphosphinimino)-ethane group is bridging two ReO3 units.
[2+3]-Cycloadditionsreaktionen von Nitrilen mit Bis(triphenylphosphoranyliden)iminiumazid/[2 + 3]Cyclo-Addition Reactions of Nitriles with Bis(triphenylphosphoranyliden)iminium Azide
Authors: Sundermeyer Jörg , Roesky Herbert W. , Noltemeyer Mathias
Published: March 2015

Cyanogen and the two isomers of S(CN)4 ((2) and (3)) react with [Ph3PNPPh3]+N3
-

(Ph3PNPPh3 equals PPN) or [Me4N]+N3
- to yield the tetrazolides [PPN]+[C2N5]- (4), [PPN]+[C4N7S]- (5), isomer (6) and [Me4N]+[C4N7S]- (7), respectively. The X-ray structure of (7) is reported. The [C4N7S]- anion is completely planar. It consists of two five-membered rings. Pyrolysis of (7) in an FD mass spectrometer gives anions of composition [C4N5]- and [C6N5]- .
Gold Complexes with Selenium Ligands, II [1] Preparation and Crystal Structures of the Gold Diphenylselenide Complexes Ph2SeAuCl and Ph2SeAuCl3
Authors: Jones Peter G. , Thöne Carsten
Published: March 2015

The complexes Ph2SeAuCl (green) and Ph2SeAuCl3 (brown) are prepared by direct reaction between the diphenylselenide ligand and the corresponding gold chloride. The crystal structures confirm the presence of monomeric, linear (AuI) or square planar (AuIII) coordinated complexes with bond lengths A u(I)-Se 2.378(1), Au(III)-Se 2.445(1) Å. Short non-bonded contacts Au(I) ··· Au(I) and Au(III) ··· Cl are observed.
Darstellung und Charakterisierung eines Technetium-Butadien-Komplexes; Röntgenstrukturanalyse von [Tc2(CO)8][μ-C4H6]
Authors: Kanellakopulos Basil , Nuber Bernhard , Raptis Konstantinos , Ziegler Manfred L.
Published: March 2015

(4).

Tc2(CO)10 has been photolyzed in the presence o f butadiene at - 20 °C in pentane. Under these conditions the only product which could be characterized is the complex [Tc2(CO)8][μ-C4H6] The X -ray structure determination shows that 1 is isomorphous with the homologues species [M2(CO)8][μ-C4H6] (M = Mn, Re) with the trans-butadiene ligand bridging the two technetium centers. 4 is compared to the manganese (5) and rhenium species (6 ).
Einfluß der Dotierung von BaPb0,75Bi0,25O3 mit K, Rb und Cs auf dessen supraleitende Eigenschaften
Authors: Jansen M. , Bredthauer J.
Published: March 2015

x

In the series with nominal stoichiometry Ba1-xAxPb0,75Bi0,25O3 (A = K, Rb with = 0.1, 0.2, 0.3, and A = Cs with x = 0.1) solid solutions were prepared. The composition of the samples obtained was verified by X -ray techniques. All compounds crystallize tetragonally with a 3-dimensional array of Pb(Bi) - O6 octahedra and Pb(Bi) -O -Pb(Bi) bonding angles of 180° (c-axis) and 165° (xK = 0.3) 168° (xRb = 0.3 and xCs = 0.1) within the a/b plane. Superconducting transition temperatures o f Ba1-xAxPb0,75Bi0,25O3 with Te = 12 (“onset”) were determined using a SQUID magnetometer.
Kupplungsreaktionen von Diazoniumsalzen mit 2,7-Methanoaza[10]annulen und Röntgenstrukturanalyse eines Vertreters
Authors: Neidlein Richard , Johmann Andrea A. , Boese R.
Published: March 2015

X -ray analysis of the first azo-dye stuff of 2,7-methanoaza[10]annulene is reported.
Synthesis of Amino Acids Analogues of Citric Acid Siderophores
Authors: Milewska Maria J. , Chimiak Andrzej , Neilands John B.
Published: March 2015

2-tert-buiyl-

Three amino acid analogues of citric acid siderophores were synthesized. The synthetic strategy involved condensation of 2-tert-butyl-1,3-di(N-hydroxysuccinimidyl) or 1,3-bis(pentachlorophenyl)citrates with N-ethyl-ω-aminoalkylhydroxamates. The examination of biological properties of the obtained compounds revealed their poor, if any siderophore activity and thus confirmed the structural requirements previously suggested for siderophores of this type.
I(E)-l,2-Difluoro-2-(pentafluoro-λ6-sulfanyl)ethenyl]phosphonates
Authors: Wessolowski Holger , Röschenthaler Gerd-Volker , Winter Rolf , Gard Gary L.
Published: March 2015

For the first time SF5 containing organic phosphonates, SF5CF = CFP(O)(OR1)2 have been prepared from trimethylsilylphosphites, (R1O)2POSiMe3 (R1 = Et, R1 = SiMe3) and trifluorovinylsulfur pentafluoride, SF5CF = CF2 in an Arbuzov type reaction.
Über den Einbau von AI(III), Ga(III) und In(III) in das Calcium-Fluorapatit-Gitter
Authors: Manca S. G. , Urquiza N. , Baran E. J.
Published: March 2015

In order to determine the effect of Al(III), Ga(III) and In(III) on the inorganic phase of bone, a model study has been undertaken, investigating a series of fluoroapatites in which part of the Ca(II) ions were substituted be these cations. Diffractometric and spectroscopic studies show that low concentrations of the incorporated metals neither affect the crystallographic characteristics nor the strength of the P - O bonds of these apatitic materials.
Synthese und Kristallstruktur von [LiCl · 2THF]2 / Synthesis and Crystal Structure of [LiCl · 2THF]2
Authors: Hahn F. Ekkehardt , Rupprecht Stefan
Published: March 2015

The reaction of lithiated catechol ligands with W (0)Cl4 produces LiCl as a side product. The lithium chloride from this reaction crystallizes as (THF)2Li(μ-Cl)-,Li(THF)2. The X -ray analysis shows lithium in the center of a distorted tetrahedron made up from two THF molecules and two bridging chlorides with d(Li-Cl) = 2.342(3) and 2.308(3)Å.
Kristallstruktur-V erfeinerungen an Rubidiumtetr afluorometallaten(II): Rb2MF4 (M = Mg, Co, Ni) / Crystal Structure Refinements at Rubidiumtetrafluorometallates(II): Rb2MF4 (M = Mg, Co, Ni)
Authors: Welsch Matthias , Babel Dietrich
Published: March 2015

The tetragonal K2NiF4 type crystal structure (I4/mmm , Z = 2) has been refined at isostructural Rb2MgF4 (a = 405.5, c = 1379.0 pm , w R = 0.083), Rb2CoF4 (a = 414.9, c = 1369.6 pm, w R = 0.045) and Rb2NiF4 (a = 408.6, c = 1370.8 pm , w R = 0.023), using between 169 and 313 independent single crystal X-ray reflections. In contrast to the anomaly of nearly undistorted MF6 octahedra in the potassium compounds K2MF4, significant shortening o f the terminal vs. bridging bonds is observed in Rb2MF4: Mg - F = 199.3/202.8, C o - F = 202.8/207.5, Ni - F = 200.7/204.3 pm .
Säure-induzierte CC-Kupplung von Isocyanid-Liganden in homoleptischen Alkylisocyanid-Komplexen von Mo(0) und W(0) / Acid-Induced CC-Coupling of Isocyanide Ligands in Homoleptic Alkylisocyanide Complexes of Mo(0) and W(0)
Authors: Filippou Alexander Constantin , Grünleitner Walter
Published: March 2015

Reactions of the electron-rich, homoleptic alkylisocyanide complexes M(R N C)6 (1a-2b) (1: M = Mo, 2: M = W; a: R = Et, b: R = tBu) with electrophiles have been studied. A coupling of two isocyanide ligands to a complexed alkyne ligand is observed, when M(R N C)6 is treated with two equivalents of HX(X = Br, I) and leads to the bis(alkylamino)acetylene complexes [X (R N C )4M[η2-R(H)NC ≡ CN(H)R]]X (3a′-4b″) (3: M = Mo, 4: M = W). Treatment of W (EtNC)6 (2a) and W (tBuNC)6 (2b) with one equivalent of Me3SiOTf results in the quantitative formation of the aminocarbyne complexes [(EtNC)5W ≡ CN (SiMe3)Et]OTf (6c) and [(tBuNC)5W ≡ C N (SiMe3)tBu]OTf (6d), respectively. In comparison, an equilibrium between W(tBuNC)6 (2b) and the aminocarbyne complex [(tBuNC)5W ≡ C N (SiMe3)tBu]Cl (6e) is found, when 2b is treated with Me3SiCl. The compounds 6c and 6d are structurally related to the aminocarbyne complexes [(EtNC)5M ≡ C N E t2]BF4 (5a: M = Mo, 6a: M = W) and [(tBuNC)5W ≡ C N (Et)

Bu]BF4 (6b), which are obtained from ethylation of M (EtNC)6 (1a, 2a) and W (tBuNC)6 (2b) with Et3OBF4. 5a and 6a undergo with HI a carbyne-isocyanide coupling reaction to give the alkyne complexes [I(EtNC)4Mo[η2-Et2NC≡CN(H)Et]]BF4 (7a) and [I(EtNC)4W[η2-Et2NC≡CN(H)Et]]BF4 (8a), respectively. Similar reactivity is exhibited by 6b, which yields with HI the alkyne complex [I(tBuNC)4W[η2-tBu(Et)N C ≡ C N (H)tBu]]BF4 (8b). The reported transformation of a complexed isocyanide to an aminocarbyne and the acid-induced aminocarbyne-isocyanide coupling reaction are experimentally verified to be important steps in the reductive coupling of isocyanide ligands in [M(RNC)6X]+-complexes yielding the bis(alkylamino)acetylene compounds [X(R N C)4M[η2-R (H )N C ≡ C N (H )R ]]+.
Impedanzmessungen an Tetraiodomercuraten/Impedance Spectroscopy of Tetraiodomercurates
Authors: Brodersen K. , Göhr H. , Schrenk J.
Published: March 2015

As thermochromic compounds, tetraiodomercurates show phase transitions, which have been investigated by impedance spectroscopy. In the case of Ag2HgI4 and Cu2HgI4 we found clear changes of conductivity not present with HgI2. In all cases the main resistance is caused by the grain boundaries between the single crystals of the powder sample. Also diffusion in the double layer in front of the surface of the electrodes influences the spectra. Single crystal measurements of Hgl, show the different ionic mobilities along the various crystallographic directions.
Darstellung und spektroskopische Charakterisierung von Methoxysulfoniumsalzen. R2SOCH3
+X-(R = F, Cl, CF3, CH3; X- = AsF6
-, SbF6
-, Sb2F11
- )/Preparation and Spectroscopic Characterization of Methoxysulfonium Salts. R2SOCH3
+X- (R = F, CI, CF3, CH3; X- = AsF6
-, SbF6
- , Sb2F11
-)
Authors: Minkwitz Rolf , Molsbeck Walter
Published: March 2015

The preparation of the sulfonium salts R2SOCH3
+X- (R = F, Cl, CF3, CH3; X- = AsF6
-, SbF6
-, Sb2F11
-) is reported. The compounds have been obtained from the sulfuranes R2SO with reagents CH3OSO+MF6
- (M = As, Sb) in liquid SO2 and characterized by Raman and 1H , 13C, and 19F NMR spectroscopy.
Lithiumverbindungen von Adamantyl-, Silyl- und Arylaminofluorsilanen/Lithium Compounds of Adamantyl-, Silyl- and Arylaminofluorosilanes
Authors: Klingebiel U. , Stalke D. , Vollbrecht S.
Published: March 2015

Dimeric lithium-adamantylimino-di-tert-butylfluorosilane, [(Me3C)2 SiF Li N Ad]2, adds one molecule of THF per dimer when crystallized from THF. A bicyclic compound is obtained with four- [F2Li(THF)N] and two-coordinated [NLiN] lithium. Lithiated di-tert-butyl-[{tert-butyldiphenylsilyl)]aminofluorosilane and di-ter-butyl-4-fluoroanilinofluorosilane both add two molecules of THF with formation of (SiFLi(THF)2N)-four-membered rings when crystallized from THF. THF can be replaced by TMEDA with retention of the (SiFLiN )- four-membered ring. The crystal structure of (Me3C)-,SiFLi(TMEDA)NC6H4F is reported.
Übergangsmetallkomplexe mit Schwefelliganden, LXXX. Synthese, Struktur, Oxotransfer- und redoxgekoppelte Kondensationsreaktionen von Molybdän-Oxo-Komplexen mit dem sterisch anspruchsvollen vierzähnigen Thioether-Thiolat-Liganden 'buS4'2- ('buS4'2- = 1,2-Bis(2-mercapto-3,5-di-t-butylphenylthio)ethan(2—))/Transition Metal Complexes with Sulfur Ligands, LXXX. Syntheses, Structures, Oxo Transfer and Redox Coupled Condensation Reactions of Molybdenum Oxo Complexes with the Sterically Demanding Tetradentate Thioether-Thiolato-Ligand 'buS4'2- ('buS4'2- = 1,2-Bis(2-mercapto-3,5-di-/-butylphenylthio)ethane(2—))
Authors: Sellmann Dieter , Grasser Franz , Knoch Falk , Moll Matthias
Published: March 2015

In order to obtain soluble molybdenum sulfur oxo complexes, [Mo(O)2('buS4')] (1) ('buS4'2- = 1,2-bis(2-mercapto-3,5-di-t-butylphenylthio)ethane(2-)) was synthesized by reaction of [Mo(O)2(acac)2] (acac- = acetylacetonate(1-) ) with 'buS4'-Li2. Treatment of 1 with PPh3 yielded [μ-O{Mo(O)('buS4')}2] (2) and OPPh3 in an oxo transfer reaction. [Mo(PMe3)2('buS2')2] (3) ('buS2'2- = 3,5-di-t-butyl-1,2 -benzenedithiolate(2-)) was obtained by twofold desoxygenation of 1 with excess PMe3 via a redox coupled addition elimination reaction. 2 reacts with the oxo group donor DMSO to yield 1 and Me2S. The system 1/2 then catalyses the oxo transfer reaction from DMSO to PPh3 and, therefore, shows properties modelling the co-factor in oxotransferases. In contrast to the parent compound [Mo(O)2('S4')] ('S4'2- = 1,2-bis(2-mercaptophenylthio)ethane(2-)), 1 is reactive towards hydrazine and its derivatives. Reactions with hydrazine and alkylhydrazines yield mixtures of products not containing nitrogen. By treatment of 1 with phenylhydrazine, the phenyldiazenido(1-) complex [Mo(NNPh)2('buS4')] (4) was formed in a redox coupled condensation. According to the X-ray structure analyses of 1, 2 and 4, the molybdenum centres in these complexes are coordinated pseudo-octahedrally by the four S-donors of the 'buS4'2- ligands, the oxo- and the N -donors.
Homoleptische Carbenkomplexe, IV. Tetrakis(N-alkylimidazolin-2-yliden)palladium and -platin/Homoleptic Carbene Complexes, IV. Tetrakis(N-alkylimidazolin-2-ylidene)palladium and -platinum
Authors: Fehlhammer Wolf Peter , Bliß Thomas , Fuchs Joachim , Holzmann Gerhard
Published: March 2015

Homoleptic complexes of palladium and platinum containing carbenoid imidazole ligands (1, 12-19 ) have been synthesized either directly from C2-lithiated N-methyl-imidazole and Pdl2 or, indirectly (and more efficiently), from isocyanides and 2-am inoacetaldehyde diethylacetale in the presence of Pdl2, Ptl2 or K2PtCl4 via the respective “ open chain” diaminocarbenes 2-11. Selected IR , NMR (1H , 13C), and pos-FAB mass spectrometric data of the new compounds are reported. The X-ray structure analysis of tetrakis(N -methylimidazolin-2-ylidene)palladium-diiodide (lb ) reveals a geometry of the heterocyclic ligands which deviates considerably from the one expected for extensive 6π-electron delocalization across the ring.
Synthese, Struktur und Eigenschaften der Nonachloroditellur(IV)- und Tetrachlorohydroxotellur(IV)säure-Hydrate. Kristallstrukturen der Oxonium-Salze [H9O4]n[Te2Cl9]n und [H9O4][TeCl4OH ] · H2O/Synthesis, Structure and Properties of Nonachloroditellurous and Tetrachlorohydroxotellurous Acid Hydrates. Crystal Structures of the Oxonium Salts [H9O4]n[Te2Cl9]n und [H9O4][TeCl4OH ] · H2O
Authors: Krebs Bernt , Bonmann Stefan , Gretenkord Klaus
Published: March 2015

Light yellow needles of crystalline nonachloroditellurous acid with the formal composition HTe2Cl9 · 4H2O (1) (space group C2/c, a = 11.642(6), b = 13.012(4), c = 12.663(5) Å, β = 119.64(3)° at 140 K) were isolated from a saturated solution of TeCl4 in conc. HCl. From a solution of more diluted HCl the acid HTeCl4OH · 5H2O (2) could be prepared (space group P212121, a = 7.065(3), b = 8.551(2), c = 18.192(6)Å at 140 K). 1 is the first acid isolated from the system TeCl4 /HCl/H2O with a polymeric anion. The novel polynuclear [Te2Cl9]n
n- chains are built from alternately corner-sharing and edge-sharing distorted octahedral TeCl6 units. The mean bond distances are 2.356 Å for terminal Te-Cl and 2.805 Å for Te-μ2Cl. 2 contains square-pyramidal [TeCl4OH]- anions with oxygen in the apical position (Te-Cl: 2.447-2.552 Å; Te-O: 1.926 Å). The cations in both structures are [H9O4]+ hydroxonium ions (O···O (1): 2.47(3), 2.55(2) and 2.57(1) Å; O···O (2): 2.550(4), 2.584(4) and 2.588(5) Å). Thus the formulae of the acids have to be written as [H9O4]n[Te2Cl9]n and [H9O4][TeCl4OH] · H2O. Raman spectra of both compounds are reported.
Alternativ-Liganden, XXVII. Neue zweizähnige Phosphanliganden mit M'R2-Akzeptorzentren (M' = Si, Ge; R = Me, Ph)/Alternative Ligands, XXVII. Novel Bidentate Phosphane Ligands with M'R2 Acceptor Centres (M' = Si, Ge; R = Me, Ph)
Authors: Grobe Joseph , Krummen Anita
Published: March 2015

Dipod ligands R2M'(OCH2PMe2)x(CH2CH2PMe2)2-x (R = Me, Ph; M' = Si, Ge; x = 0 - 2) have been prepared by reacting R2M'Cl2 and R2M'ClxVi2-x (x = 0, 1), respectively, with Me2PCH2OH in the presence of trimethylamine, in case of the resulting vinyl-M' derivatives R2M'(OCH2PMe2)xVi2-x (x = 0, 1) followed by the photochemical addition of Me2PH to the vinyl groups. Analytical (C, H) and spectroscopic (NMR, MS) investigations prove the purity and identity of the new donor/acceptor ligands.
Synthesis and Characterization of Cobalamines with Phosphonito and Phosphinito Ligands
Authors: Jónsdóttir Sigrídur , Klar Günter
Published: March 2015

Reactions of aquacobalamine with dimethyl and diphenyl phenylphosphonite and with methyl diphenylphosphinite lead to neutral complexes in which the partially hydrolyzed an ionic ligands [PPh(OR)(O)]- (R = Me, Ph) and [PPh2(O)]- are P-bonded to the cobalt(III) ion of the cobalamine moiety. Hydrolysis of the prochiral phosphonite already coordinated to the chiral cobalamine leads to two diastereomers which are formed in different yields. This optical induction is seen in the 1H and 31P{1H} N M R spectra.
Bicyclo[2.2.2]octane-2-spirocyclohexanes, Part 3. Synthesis and Reactions of Mono- and Dibromospirodiisophoranes
Authors: Kurzer Frederick , Kapadia Zakir
Published: March 2015

Halogenation by the appropriate amounts of bromine or N-bromosuccinimide converts spirodiisophora-3',6-dione successively into the 4'-ax-mono- and 2',4'-diax-dibromo-3',6-dione. The latter is reduced by lithium aluminium hydride to the corresponding 6,3'-ketol. with retention of one or both bromo-substituents, depending on conditions. The bromoketones undergo the Favorski ring-contraction under the influence of alkalis to compounds of the bicyclo[2.2.2]octane-2-spirocyclopentane ring-system . The 13C NMR spectra of the individual products are assigned and correlated with their structures.
Darstellung und Charakterisierung einiger ω -Cyanalkyldiorganophosphane Preparation and Characterization of Some ω - Cyanoalkyldiorgano Phosphines
Authors: Wolfsberger Werner , Burkart Wolfgang , Werner Helmut
Published: March 2015

Several routes for the preparation of ω-cyanoalkyldiorgano phosphines RR′P (CH2)nCHR″CN (R = CH3, C2H5, C3H7, i-C3H7, C4H9, i-C4H9, t -C4H9, C5H11, c-C5H9, c-C6H11 ; R′ = i-C3H7, t-C4H9, C6H5; R″ = H, Si(CH3)3; n = 1, 2, 3, 4) have been investigated: (1) reaction of lithium diorganophosphides with ω-chloroalkylnitriles, (2) quaternization of secondary phosphines with co-haloalkylnitriles followed by deprotonation of the resulting H -phosphonium halides with aqueous bases, (3) hydrophosphination of secondary phosphines with unsaturated nitriles, (4) reaction of trimethylsilyl phosphines with (y-chloroalkylnitriles followed by Me3SiCl-elimination, and (5) addition of acrylonitrile to trimethylsilyl phosphines. The reaction of 3-chloropropionitrile with trimethylsilyl phosphines leads to the formation of a mixture of the expected phosphine and the corresponding β-silylated derivative. A mechanistic interpretation of the last reaction is given. All new compounds were characterized by elemental analyses, IR and NMR spectra.
Hinweise zur thermodynamischen Kontrolle von relativen Hydriergeschwindigkeiten an Platin Indications to a Thermodynamic Control of the Relative Rate of Hydrogenation on Platinum
Authors: Maier Wilhelm F. , Etzkorn Felicia A.
Published: March 2015

The relative rate of hydrogenation of various alkenes has been determined by competition experiments in the gas phase on platinum films. Despite big structural differences in the alkenes there is a good correlation of the relative rate of hydrogenation with the calculated heat of hydrogen atom addition to the double bond, indicating thermodynamic control of this reaction.