bluuebunny/crossref_metadata_2025_split huggingface dataset:
Elektrochemische Untersuchungen an Graphitsalzen mit HNO3, HClO4, HReO4 und halogenierten Essigsäuren / Electrochemical Investigations on Graphite Salts with HNO3, HClO4, HReO4 and Halogenated Acetic Acids
Authors: Scharff Peter 
Published: March 2015

HNO3, HClO4, HReO4 and CF3COOH have been intercalated into graphite by anodizing pieces of HOPG. Attempts to intercalate ClCH2COOH have failed.
CV measurements and pulsed galvanostatic experiments were performed to ascertain possible side reactions as well as the reversibility of the intercalation process.
Whereas the intercalation reaction proved to be fast in the cases of HNO3, HClO4 and HReO4, it was slow and superposed by side reactions when CF3COOH was used.
127I, 185Re and 187Re Solid State NMR Measurements on (CH3)4AsIO4 and (CH3)4AsReO4
Authors: Grommelt M. , Burkert P. K. 
Published: March 2015

Tetramethylarsonium-metaperiodate shows 127I solid state NMR signals without any visible quadrupole splitting. Due to the very large nuclear quadrupole moments of the rhenium isotopes 185,187Re, the analogous Re compound exhibits the expected second order quadrupole NMR effects. The measured 185,187ReRe NMR powder spectra contain superimposed signals arising from two different types of ReO-
4 tetrahedra, indicating that part of the ReO4
- anions deviate only slightly from tetrahedral symmetry, while the other part are nearly undistorted ReO4
- anions.
The temperature dependence of the solid state NMR spectra reveals phase transitions for both compounds, which are confirmed also by DSC analyses. Furtherm ore, the DSC analysis of the Re compound again proves the existence of the two different types of ReO4
- tetrahedra in the lattice of the high temperature modification.
Cyclische Diazastannylene, XXX [1] Symmetrisch und asymmetrisch substituierte German- und Stannandiyle mit Amid-, Alkoholat- und Thiolat-Liganden, Teil I [2] / Cyclic Diazastannylenes, XXX [1] Symmetrically and Asymmetrically Substituted Germane- and Stannanediyls with Amide, Alcoholate and Thiolate Ligands, Part I [2]
Authors: Veith M. , Hobein P. , Rösler R. 
Published: March 2015

Chelates of Ge(II) and Sn(II)
Symmetrically and unsymmetrically substituted germane- and stannanediyls as well as chelated bis(amino)- or aminooxogermanium- and -tinmonohalides have been obtained from cyclic bis(amino)germane- and stannanediyls by treatment with tert-butylamine, tert-butanol and tert-butylmercaptane. The following compounds have been synthesized: GeX2 (X = OtBu (5), StBu (6)), Sn(StBu), (9), GeXCl (X = N(H)tBu (21), OtBu (22)), SnXCl (X = N(H)tBu (23), OtBu (24), StBu (25), OMe (28)) and Sn(OtBu)Br (27). In the series of the chelates Me2Si(NtBu)(NHtBu)GeCl (13), Me2Si(NtBu)(OtBu)SnX (X = Cl (18), OMe (19)) and the bischelate [Me2Si(NtBu)(OtBu)]2Sn (20) have been prepared. When 18 is allowed to react with aluminiumtrimethyl Me2Si(NtBu)(OtBu)AlClMe is formed, a compound with a center of chirality at the aluminium atom. X-ray structure determinations have been performed on single crystals of 6, 8, 9, 13, 22 and 24. 6, 8, 22 and 24 form molecular dimers with c.n. of 3 at the Ge or Sn atoms, resp. While the tBu-S ligands are syn with respect to the central Ge2S2 ring in 6 (symmetry approaching C2v), the tBu-O ligands are anti to the central Sn2O2 ring in 8 (symmetry Ci). 9 forms a coordination polymer with all Sn atoms in a Ψ-trigonal-bipyramidal and all S atoms in a Ψ-tetrahedral environment. The germanium atom in 13 is coordinated by a chlorine, a λ3- and a λ4-nitrogen atom, the two nitrogen atoms being connected by as dimethylsilyl group. The hydrogen and chlorine atom of 13 are found at the same side of the four-membered chelate ring. The two unsymmetrically substituted, homologous compounds Ge(O/tBu)Cl (22) and Sn(OtBu)Cl (24) are found to form dimers via O→Ge resp. O→Sn bonds. While the chlorine atoms in 22 are syn with respect to the four-membered ring, they are anti in the case of molecule 24.
[Na-15-Krone-5]2[ZrF2Cl4] und (PPh4)2[ZrCl6] · 2 CH2Cl2; Synthesen, IR-Spektren und Kristallstrukturen / [Na-15-Crown-5]2[ZrF2Cl4] and (PPh4)2[ZrCl6] · 2 CH2Cl2; Syntheses, IR Spectra, and Crystal Structures
Authors: Hartmann Eva , Dehnicke Kurt , Fenske Dieter , Goesmann Helmut , Baum Gerhard 
Published: March 2015

[Na-15-crown-5]2[ZrF2Cl4] has been prepared by the reaction of the amidinato complex [Ph—C(NSiMe3)2ZrCl3]2 with sodium fluoride in acetonitrile suspension, as well as by the reaction of ZrCl4 in acetonitrile, both in the presence of 15-crown-5. On an analogous route (PPh4)2[ZrCl6] · 2 CH2Cl2 has been prepared by the reaction of [Ph—C(NSiMe3)2ZrCl3]2 with PPh4Cl in CH2Cl2 solution, as well as by the reaction of ZrCl4 with PPh4Cl in CH2Cl2. The compounds are characterized by their IR spectra and by crystal structure determinations.
[Na-15-crown-5]2[ZrF2Cl4]: Space group Ρ21/a, Z = 4, 6589 observed independent reflexions, R = 0.069. Lattice dimensions at 20°C: a = 1705.0(9), b = 1092.4(6), c = 1906.5(10) pm, β = 113.14(3)°. [Na-15-crown-5]2[ZrF2Cl4] forms ion triples, in which both sodium ions are sevencoordinate by five oxygen atoms of the crown ether molecules, as well as by a fluorine and a chlorine atom of the cis-[ZrF2Cl4]2- unit.
(PPh4)2[ZrCl6] · 2 CH2Cl2: Space group P1̄, Z = 1, 4831 observed independent reflexions, R = 0.041. Lattice dimensions at 20°C: a = 1030.1(5), b = 1124.8(6), c = 1245.6(6) pm, α = 70.81(3), β = 80.61(4), γ = 80.39(4)°. The compound has an ionic structure with ZrCl6
2- ions of symmetry Ci.
Darstellung und Kristallstruktur zweier Polytelluride mit großen mehrfach geladenen Kationen / Determination and Crystal Structure of Two Polytellurides with Large Double and Triple Charged Cations
Authors: Klinkhammer K. W. , Böttcher P. 
Published: March 2015

Two polytellurides of double and triple charged organic cations have been synthesized and their crystal structures have been determined.
K2Te3 and the iodides of 2,2,5,5-tetramethyl-2,5-diazoniahexane, [TMDH]I2, and 2,2,5,5,8,8-hexamethyl-2,5,8-triazonianonane, [HMTN]I3, respectively, are mixed together in aqueous solution in appropriate ratios. After a few hours black crystals of the polytellurides precipitate. The reaction of the double charged cation, TMDH2+, results in the tetratelluride, [TMDH]Te4, whereas that of the triple charged cation, HMTN3+, gives the tridecatelluride, [HMTN]2Te13.
[TMDH]Te4 crystallizes in the space group P21/n (a = 13.321(5) A, b = 15.940(7) A, c = 7.969(3) Å, β = 94.12(3)°). Interconnected Te4
2--polyanions are found in the structure. [HMTN]2Te13 crystallizes in the space group PĪ (a = 8.772(2) Å, b = 17.529(4) Å, c = 18.036(4) Å, a = 68.11(3)°, β = 76.73(3)°, γ = 77.08(3)°). No distinct tridecatelluride polyanions occur in the structure, but rather two crystallographically independent Te4
2--anions and one Te5
2--anion. As in [TMDH]Te4, all of the anions are interconnected.
Synthesis and Plane Selective Spin Trapping of a Novel Trap 5,5-Dimethyl-3-(2-ethoxycarbonylethyl)-1-pyrroline N-oxide
Authors: Zhang Yong-Kang , Lu Dao-Hui , Xu Guang-Zhi 
Published: March 2015

A novel cyclic nitrone spin trap 5,5-dimethyl-3-(2-ethoxycarbonylethyl)-1-pyrroline N-oxide has been prepared and its ability to trap a series of transient free radicals has been investigated. This nitrone scavenges free radicals to give persistent nitroxides, e.g., the half life-times of hydroxyl radical adducts and tert-butoxy radical adducts in benzene &gt;30 min, and the life-time of acetyl adducts &gt;60 min. The EPR spectrum of 2,2-dimethyl-4-(3-hydroxypropyl)pyrrolidinyl-1-oxyl aminoxyl shows that the hyperfine splitting constants of two
β-hydrogens are equal to 14.58 G and 23.29 G respectively, i.e., the two β-hydrogens are not magnetically equivalent. Radical addition to the nitrone is probably plane selective affording only one of the two possible geometric isomer pairs of the spin adduct nitroxides. The trans approach mechanism is proposed through configuration and conformation analysis.
121Sb-Mössbauer-spektroskopische und strukturchemische Untersuchungen an Kronenetherkomplexen SbX3(15-Krone-5) mit X = F, Cl, Br, I. Eine Analyse der Orbitalbesetzungszahlen / 121Sb-Mössbauer-Spectroscopic and Structural Investigations on Crown Ether Complexes SbX3(15-Crown-5) with X = F, Cl, Br, I. A Population Analysis
Authors: Schäfer Michael , Pebler Jürgen , Borgsen Beatrice , Weller Frank , Dehnicke Kurt 
Published: March 2015

The crown ether complexes SbX3(15-crown-5) with X = F, Cl, Br, and I have been prepared by reactions of 15-crown-5 with the corresponding antimony trihalides in acetonitrile solutions. The compounds were characterized by IR spectroscopy as well as by 121Sb-Mössbauer spectroscopy. A method of orbital population analysis utilizing both Mössbauer isomer shifts and quadrupole coupling has been developed for Sb(III) antimony halides and their crown ether complexes.
SbF3(15-crown-5) was also characterized by an X-ray structure determination: Space group P21/n, Z = 4, 3628 observed unique reflexions, R = 0.032. Lattice dimensions at 19 °C: a = 891.54(6), b = 1277.26(6), c = 1277.66(7) pm, β = 95.029(4)°. The complex has a molecular structure in which the antimony atom is surrounded by three F-atoms with mean bond lengths of 192.4 pm and by the five oxygen atoms of the crown ether molecule with mean bond lengths of 293.9 pm.
Synthese und Kristallstruktur des Amido-Palladats (PPh4)2[Pd2Cl4(NH2)2] · CH2Cl2 und des Benzamidin-Palladats PPh4{ [Ph– C(NH2)(NH)]PdCl3} · CH3CN / Synthesis and Crystal Structure of the Amido Palladate (PPh4)2[Pd2Cl4(NH2)2] · CH2Cl2 and of the Benzamidine Palladate PPh4{[Ph—C(NH2)(NH)]PdCl3} · CH3CN
Authors: Arnim Henning von , Massa Werner , Zinn Alfred , Dehnicke Kurt 
Published: March 2015

Orange crystals of (PPh4)2[Pd2Cl4(NH2)2] have been prepared by the reaction of (PPh4)2[Pd2Cl6] with N,N,N′-tris(trimethylsilyl)benzamidine in boiling acetonitrile in the presence of water, and orange brown crystals of PPh4{[Ph—C(NH2)(NH)]PdCl3} by the reaction of the amidinato complex PPh4[Ph—C(NSiMe3)2PdCl2] with HCl gas in acetonitrile solution. The complexes were characterized by IR spectroscopy as well as by X-ray structure determinations.
(PPh4)2[Pd2Cl4(NH2)2] · CH2Cl2: Space group PĪ, Z = 1, 2784 observed unique reflections, R = 0.043. Lattice dimensions at —60 °C: a = 1053.3(4), b = 1081.1(4), c = 1249.2(4) pm, α = 102.90(2)°, β = 110.44(2)°, γ = 102.23(2)°. The compound consists of PPh4
+ ions and centrosymmetric anions [Pd2Cl4(NH2)2]2- with bridging chlorine atoms and terminal amido groups.
PPh4{[Ph—C(NH2)(NH)]PdCl3} -CH3CN: Space group C2/c, Z = 8, 1183 observed unique reflections, R = 0.033. Lattice dimensions at —60 °C: a = 3106.7(6), b = 1059.0(1), c = 1818.0(4) pm, β = 90.98(2)°. The compound consists of PPh4
+ ions, [Ph—C(NH2)(NH)PdCl3]-ions, and included CH3CN molecules. In the anion the benzamidine ligand is bound via the nitrogen atom of the imido group.
Neue mehrkernige Pd-Komplexe mit S, Se und PPh3 als Liganden. Die Kristallstrukturen von [Pd5Se4Cl2(PPh3)6], [Pd4NiS4Cl2(PPh3)6], [Pd5Se5(PPh3)5], [Pd6Se4Cl4(PPh3)6], [Pd7Se6(SeH)Cl(PPh3)7], [Pd8Se8(PPh3)8] und [Pd8Se8Cl(PPh3)8] + [CpCrCl3]- / New Multinuclear Pd Complexes with S, Se and PPh3 as Ligands. The Crystal Structures of [Pd5Se4Cl2(PPh3)6], [Pd4NiS4Cl2(PPh3)6], [Pd5Se5(PPh3)5], [Pd6Se4Cl4(PPh3)6], [Pd7Se6(SeH)Cl(PPh3)7], [Pd8Se8(PPh3)8] and [Pd8Se8Cl(PPh3)8]+[CpCrCl3]-
Authors: Fenske Dieter , Fleischer Holm , Krautscheid Harald , Magull Jörg , Oliver Christopher , Weisgerber Sabine 
Published: March 2015

[PdCl2(PPh3)2] reacts with Se(SiMe3)2 to form a mixture of multinuclear Pd complexes, [Pd3Se2(SeSiMe3)2(PPh3)4] (1), [Pd5Se5(PPh3)5] (2) and [Pd8Se8(PPh3)8] (3). 1 can be used as starting material for the synthesis of further Pd clusters. Reactions of 1 with [CpCrCl2(THF)], [PdCl2(PPh3)2] and [NiCl2(PPh3)2] lead to the formation of [Pd6Se4Cl4(PPh3)6] (4), [Pd8Se8Cl(PPh3)8]+[CpCrCl3]- (5), [Pd5Se4Cl2(PPh3)6] (6) and [Pd7Se6(SeH)Cl(PPh3)7] (7). The complexes [Pd6Se4(SeH)2Cl2(PPh3)6] and [Pd6Se4(SeH)4(PPh3)6] have structures similar to 4, and are formed by reaction of [PdCl2(NBD)] or [PdCl(COD)]2(BF4)2 with PPh3 and Se(SiMe3)2.
Reaction of [(C3H5)PdCl]2 with [NiCl2(PPh3)2] and S(SiMe3)2 leads to the formation of the heterometal cluster [Pd4NiS4Cl2(PPh3)6] (8).
The molecular structures of 2-8 show quite clearly that these compounds may be considered as intermediates on the route towards multinuclear Pd complexes.
Übergangsmetallkomplexe mit Schwefelliganden, LXXIII. Diastereospezifische Dichlormethylierung schwefelreicher [RuII(SRR′)(PPh3)′S4]-Komplexe (SRR′ = einzähniger Thioether- oder Thiol-Ligand; ′S4′2- = 1,2-Bis(2-mercaptophenylthio)ethan(2-)) / Transition Metal Complexes with Sulfur Ligands, LXXIII. Diastereospecific Dichloromethylation of Sulfur Rich [RuII(SRR′)(PPh3)′S4] Complexes (SRR′ = Monodentate Thioether or Thiol Ligand;′S4′2- = 1,2-Bis(2-mercaptophenylthio)ethane(2-))
Authors: Sellmann Dieter , Lechner Peter , Knoch Falk , Moll Matthias 
Published: March 2015

Under exclusion of air the thioether and thiol complexes [Ru(SRR′)(PPh3)′S4′] (′S4′2- = 1,2-bis(2-mercaptophenylthio)ethane (2—)) easily react with CHCl3 yielding [Ru(Cl)(PPh3)(′S4′—CHCl2)] in which one thiolato atom of the ′S4′ ligand is diastereospecifically dichloromethylated. In the presence of air, however, [RuIII(Cl)(PPh3)′S4′] is formed.
The molecular structures of [Ru(Cl)(PPh3)(′S4′-CHCl2)] · 2CHCl3 and [RuIII(Cl)(PPh3)′buS4′] have been determined by X-ray crystallography. ′buS4′2- (= 1,2-bis(3,5-di(t-butyl)-2-mercaptophenylthio)ethane(2-)) is the t-butyl derivative of the ′S4′ ligand. Reasons for observed diastereospecifity of alkylation are discussed.
Darstellung und Kristallstruktur von Na4Ga2S5. Ein Thiogallat mit -Zweier-Doppelketten / Preparation and Crystal Structure of Na4Ga2S5. A Thiogallate with --zweier-Double Chains
Authors: Klepp Kurt O. 
Published: March 2015

Transparent single crystals of Na4Ga2S5 were obtained from a melt of Na2S, Ga and S. Na4Ga2S5 is monoclinic, space group P21/c with a = 7.967(1), b = 6.133(2), c = 19.852(9) Å, β = 91.61(2)°, Ζ = 4. Its crystal structure was refined to a conventional R of 0.033 for 1150 observed reflections.
The structure of Na4Ga2S5 is of a new type. It is characterized by infinite ribbon like thiogallate anions,

-, which are built up by GaS4-tetrahedra (mean Ga-S bond length 2.28 A) sharing apices and edges. The four crystallographically independent alkali cations are coordinated to six sulphur atoms in distorted octahedral configurations.
Synthese und Struktur der Basenaddukte von Kupfer(I)-Halogeniden mit Dimethylsulfid und Tetrahydrothiophen / Synthesis and Crystal Structure of Lewis Base Adducts of Copper(I)-Halides with Dimethylsulfide and Tetrahydrothiophene
Authors: Maelger Harald , Olbrich Falk , Kopf Jürgen , Abeln Dirk , Weiss Erwin 
Published: March 2015

Copper complexes of the general formula [(CuX)a(L)b]n with L = tetrahydrothiophene (THT) or dimethylsulfide (DMS) and X = Cl, Br or I are formed by direct reaction of copper(I)halides with the corresponding ligands. All compounds have been characterized by X-ray crystallography. [(CuCl)(dms)]„ (la) crystallizes in the monoclinic space group P 21/c (a = 762.6(1), b = 638.0(2), c = 1154.8(3) pm, β = 108.10(2)° and Ζ = 4), [(Cul)(dms)1.5]n (le) in Ι 2/a (a = 1202.9(2), b = 780.0(2), c = 1714.6(2) pm, β = 97.92(2)° and Ζ = 8), [(CuCl)(tht)1.5]n (2a) in C 2/c (a = 1244.7(2), b = 1610.3(2), c = 988.9(2) pm,β = 111.51(1)° and Z = 8) and [(CuBr)(tht), 5]„ (2b) also in C2/c (a = 1159.6(2), b = 1638.8(3), c = 1015.1(2) pm, β= 109.44(1)° and Z = 8).
The crystal structures of [(CuBr)(dms)]„ (lb) and [(CuI)(tht)2]2 (2 c) are already known. In all structures the central copper atom is coordinated to two halide and two sulphur atoms with formation of a distorted tetrahedron. Two copper and two halogen atoms form planar Cu2X2 rings which are linked by the sulphur atoms of the thioethers. The thioether ligands can either function as bridges or they are coordinated “end on”. In la and lb a polymeric layer structure is found, while 1 c, 2a und 2b form polymeric chains. 2c forms dimers. Cu · · · Cu distances are in the range of 268.4 to 298.3 pm and Cu–S bond lengths are between 228.1 and 237.2 pm.
Nitrosolate und verwandte Verbindungen, XII Nitrosolatokomplexe von Silber(I) / Nitrosolates and Related Compounds, XII Nitrosolato Complexes of Silver(I)
Authors: Olbrich Falk , Zimmer Bärbel , Kastner Michael , Schlabrendorff Carl von , Vetter Gottlieb , Klar Günter 
Published: March 2015

X-ray analysis shows silver(I) aminomethylnitrosolate to have dimers as structural units, in which the W-shaped nitrosolate ions act as μ2-bridging ligands via the nitrogen atoms of the NO groups. The nearly planar dinuclear complexes form stacks, which are connected by additional AgO contacts leading to a kind of layer structure. These layers are held together by hydrogen bonds.
Mononuclear complexes of composition [Ag(nitrosolate)L2] can be obtained from silver(I) ethylnitrosolate and bipyridyl in methanol and from silver(I) benzylnitrosolate and triphenylphosphane in diethylether/liquid ammonia. In these complexes the nitrosolate ions are supposed to act as chelating ligands, again with N,N′-coordination.
Synthese und Charakterisierung achtgliedriger Cyclometallaphosphazene von Niob(V) und Titan(IV) sowie cyclischer und acyclischer Verbindungen von Molybdän(VI) mit Perfluoralkyl-Gruppen – Kristallstruktur von [Ph2PNONbCl3]2 · 4 MeCN / Synthesis and Characterization of Eight-Membered Dimetallacyclophosphazenes with Niobium(V) and Titanium(IV) and Cyclic as well as Acyclic Compounds of Molybdenum(VI) Containing Perfluoroalkyl-Groups – X-Ray Crystal Structure of [Ph2PNONbCl3]2·4MeCN
Authors: Olms Petra , Roesky Herbert W. , Keller Klaus , Noltemeyer Mathias 
Published: March 2015

Me3SiOPPh2NSiMe3 (1) reacts with NbCl5 and CpTiCl3 to form the eight-membered ring compounds [Ph2PNONbCl3]2 (2) and [Ph2PNOTiClCp]2 (3). The reaction of (C2F5)2P(Cl)=NSiMe3 (4) with MoO2Cl2 and MoOCl4 in CH2C12 quantitatively yields the compounds [MoOCl3-O-P(C2F5)2=NSiMe3]4 (5) and (C2F5)2P(Cl)=N-MoOCl3 (6).
Through recrystallization from MeCN, compound 2 has been isolated and characterized by means of X-ray analysis as the MeCN adduct 2 a.
Crystal Structure Investigation of Two Polymeric Chromium(III) Azide Complexes; KCr(pyridine)4(N3)4 and RbCr(pyridine)3(N3)4. A Structure Containing μ(l,3) and μ(1,1,3) Bridging Azido Ligands between Chromium and Rubidium Centered Polyhedra
Authors: Goher M. A. S. , Abu-Youssef M. A. M. , Mautner F. A. , Fritzer H. P. 
Published: March 2015

The structures of two polymeric complexes of chromium(III) azide with pyridine, KCr(py)4(N3)4 (1), and RbCr(py)3(N3)4 (2), were determined by X-ray crystallography. Crystal data: 1, C20H20N16CrK, monoclinic, space group C2/c, a = 1611.2(5), b = 1050.6(3), c = 1609.0(5) pm, β = 91.69(3)°, Ζ = 4 and Rw = 0.037 for 923 diffractometer data; 2, C15H15N15CrRb, monoclinic, space group P21/n, a = 1311.9(3), b = 1139.0(4), c = 1523.3(4) pm, β = 109.39(2)°, Ζ = 4 and Rw = 0.046 for 2336 data.
The crystal structure of 1 contains six-coordinated chromium and potassium cations with two pyridine ligands and four µ(1,3) bridging azido groups forming a three-dimensional network structure. The chromium atoms are trans-coordinated by the pyridine ligands, whereas the potassium cations are cis-coordinated. The polymeric complex 2 features di-µ(l,1,3) azido bridged CrRbN2 rings, distorted octahedral chromium(III) coordination geometry, sevencoordinated rubidium, and di-μ(1,3) azido bridges which link the binuclear RbCr(pyridine)3(N3)2 moieties into infinite chains parallel to the b axis.
Electronic Spectra and Photochemical Properties of Acetyldihydroquinolinones
Authors: Bakalova Snezhana , Kavrakova Ivanka 
Published: March 2015

The absorption and luminescence properties of 6-acetyl-2,3-dihydro-4(1H)-quinolinone are described and compared to those of the parent 2,3-dihydro-4(1H)-quinolinone. The character of the electronic transitions is determined by PPP quantum chemical calculations.
An N-acyl migration leading to the formation of 6-acetyl-2,3-dihydro-4(1H)-quinolinone takes place upon UV irradiation or heating with polyphosphoric acid of 1-acetyl-2,3-dihydro-4-(1H)-quinolinone. A radical mechanism of the photochemical rearrangement is proposed.
Notizen: Die Kristallstruktur von [CuICu211(CN)4(′N2S′)2[SCN (′N2S′ = 1-Thia-4,7-diazacyclononan) / Crystal Structure of [CuICu2
II(CN)4(′N2S′)2]SCN (′N2S′ = 1-Thia-4,7-diazacyclononane)
Authors: Wasielewski Klaus , Mattes Rainer 
Published: March 2015

The polynuclear complex
[CuICu2II(CN)4(′N2S′)2]SCN was obtained by gel diffusion of the sodium salt of 4,7-Bis(dithiocarboxylato)-1-thia-4,7-diazacyclononane and K3Cu(CN)4. Its structure consists of an infinite band of edge-sharing CuI(CuII)4 tetrahedra, where the Cu1 and CuII ions are connected via CN~ bridges. CuII is additionally coordinated by the N2S macrocycle 1-thia-4,7-diazacyclononane. Crystal data: monoclinic, space group C 2/c, a = 1936.6(4), b = 1287(3), c = 1337(2) pm, β = 133.07(2)°, Ζ = 4, 2336 reflections, 203 parameter, R (Rw) = 0.027 (0.031).
Silaheterocyclen, XXIV. / Silaheterocycles, XXIV.
Authors: Auner Norbert , Weingartner Armin W. , Herdtweck Eberhardt 
Published: March 2015

The 1-amino-2-neopentylsilenes 5-8 are formed in the reaction of LitBu with the aminovinylsilanes 1-4 in n-pentane (addition of LitBu to the vinylic double bond with subsequent 1,2-elimination of LiCl). The α-Li adducts initially formed are trapped by Me3SiOSO2CF3 to yield α-SiMe3-silanes. The silenes undergo insertion reactions into the Si—O bond of Me3SiOMe. In the absence of any trapping reagent dimerization occurs. One of the 1,3-disilacyclobutanes thus formed (15) could be examined by X-ray diffraction. Reacting with 1,3-butadienes the chlorosubstituted silenes 5 and 8 yield [2 + 2]-cycloaddition products. With 1,3-cyclohexadiene Diels-Alder adducts are also obtained, but with cyclopentadiene the [4+2] adducts are formed exclusively. Products of an ene-reaction are observed upon treatment of 2,5-norbornadiene with the silenes 5 and 8.
The methylsubstituted silene 6 does not undergo any cycloaddition reaction at all, while from silene 7 only traces of the cycloadducts are produced. Both species mainly yield the dimers. The preference for the [2+2] reaction type, exhibited by the silenes 5 and 8, is due to their polarity. The almost complete absence or low yield of any cycloaddition products from 6 or 7 can be correlated with the energy levels of their frontier molecular orbitals. The distribution of the disilacyclobutanes and cycloaddition product isomers is explained by the characteristics of the stereospecifically Ε-configurated silenes. The product distribution can also be rationalized considering the ambiphilic nature of the system ViRR′SiCl/Li1Bu.