bluuebunny/crossref_metadata_2025_split huggingface dataset:
Kristallstrukturen der selenid- bzw. sulfidverbrückten Gold(I)verbindungen [Se(AuPPh3)+
3]PF6
- und [S(AuPPh3)2] · CH2Cl2/Crystal Structures of the Selenide- and Sulphide-Bridged Gold(I) Complexes [Se(AuPPh3)3]+PF6
- and [S(AuPPh3)2] · CH2Cl2
Authors: Lensch Cornelia , Jones Peter G. , Sheldrick George M. 
Published: February 2015

Abstract
The Compound [S(AUPPh3)2] · CH2Cl2 was prepared from Ph3PAuCl and H2S in CH2Cl2 and characterised by X-ray structure determination [P21/c, a = 1851.6(4), b = 2225.1(6), c = 880.3(2) pm, β = 96.32(1)°, Z = 4, R = 0.053]. A constrained refinement of the light atom positions was necessary because of pseudosymmetry. Ph3PAuPF6 reacts with Se(Sn)(CH3)3)2 to give [Se(AuPPh3)3]+PF6- which was also characterised by X-ray methods [P1̄, a = 1539.5(6), b = 1800.5(7), c = 2289.5(9) pm, α = 89.35(3), β = 72.44(3), γ = 69.75(3)°, Z = 4, R = 0.061]. There are two formula units in the asymmetric unit. Both structures show short Au···Au contacts (ca. 300-340 pm).
Zintlphasen mit komplexen Anionen: Zur Kenntnis von Ca3AlAs3 und Ba3AlSb3/Zintl Phases with Complex Anions: On Ca3AlAs3 and Ba3AlSb3
Authors: Cordier Gerhard , Savelsberg Gerhard , Schäfer Herbert 
Published: February 2015

The new compound Ca3AlAs3 crystallizes in the orthorhombic system (space group: Pnma) with
a = 1221.2(3) pm, b = 420.1(2) pm, c = 1343.4(4) pm.
In the structure there are AlAs4-tetrahedra connected by common corners to „Einereinfach" chains.
The new compound Ba3AlSb3 crystallizes in the orthorhombic system (space group: Cmca) with
a = 2113.3(10) pm, b = 719.4(5) pm, c = 1400.9(8) pm.
AlSb4-tetrahedra are connected by common edges to isolated Al2Sb6 groups. According to the compositions and structures both compounds belong to the Zintl-phases.
Fehlordnung von Kationen und Kristallwasser bei kubischen Alkalitetrabromo- und -iodothallaten(III)/Disorder of Cations and Water Molecules in Cubic Tetrabromo- and -iodothallates
Authors: Rotter Heinz W. , Thiele Gerhard 
Published: February 2015

Abstract
Tetrabromo- and -iodothallates(III) of the alkali cations crystallise from aqueous solutions as cubic hydrates MTlX4·nH2O (M = Li, Na, K, Rb, Cs, NH4; X = Br, I; n = 1-2). The tetraiodothallates retain their cubic structure on dehydratisation, while the tetrabromothallates undergo structural changes. The X-ray structure analyses of RbTlBr4 · H2O, NH4TlBr4 · 2H2O and KTlBr4 · 2H2O (-50 °C) showed that these compounds consist of a three-dimensional framework of TlBr4 tetrahedra and MBr12 ikosahedra which reminds of zeolites. In cavities of this framework 2/3 of the alkali cations and the crystal water molecules are accommodated in a disordered manner.
Strukturuntersuchungen an Vierringsystemen, III* Kristall- und Molekülstrukturen von trans-2.4-Bis(trimethylsilyl)-2.4-dihydro- 1.3-dithietan-1.1.3.3-tetroxid, 2.2.4.4-Tetramethyl-3-pyrrolidinocyclobutanon und 2.2.4.4-Tetramethyl-1-phenyl-3-pyrrolidinoeyelobutanol/Structural Investigations on Four-Membered Ring Systems, III* Crystal and Molecular Structures of trans-2,4-Bis(trimethylsilyl)-2,4-dihydro-1,3-dithietane-1,1,3,3-tetroxide, 2,2,4,4-Tetramethyl-3-pyrrolidinocyclobutanone and 2,2,4,4-Tetramethyl-1-phenyl-3-pyrrolidinocyclobutanol
Authors: Balbach Barbara , Alt Reinhold , Ziegler Manfred L. 
Published: February 2015

Abstract
The molecular structures of the title compounds have been determined by X-ray methods. In the bis(trimethylsilyl) substituted dithietane the (CH3)3Si groups are in trans position; the C2S2-ring is planar. In the cyclobutanone the pyrrolidine group occupies an equatorial position, as does the phenyl group in the cyclobutanol. In the latter the hydroxyl group is trans to the pyrrolidine ring. The four-membered carbon rings are folded.
Synthesen und Reaktionen von schwefelkoordinierten Ruthenium-Komplexen [1]/Syntheses and Reactions of Sulfur Coordinated Ruthenium Complexes [1]
Authors: Sellmann Dieter , Böhlen Elmar 
Published: February 2015

Abstract
The syntheses and reactions of sulfur coordinated ruthenium centers with CO, PR3, (R = Me, Ø), N2H4 and N2 are investigated. Reaction of [Ru(CO)3(THF)Cl2] with lithium-o-methylthiobenzenethiolate yields cis-[Ru(CO)2(CH3S-C6H4-S)2], with Li2-o-benzenedithiolate the cis-[Ru(CO)2(C6H4S2)2]2--ion is obtained, which can be isolated either as the NMe4 salt or reacted further with 1,2-C2H4Br2 to give cis-[Ru(CO)2dttd], (dttd2-= 2,3,8,9-Dibenzo-1,4,7,10-tetrathiadecane2-). In all three complexes the CO ligands are relatively inert to substitution; refluxing of [Ru(CO)2(C6H4S2)2]2- in EtOH in the presence of excess PMe3, however, and subsequent alkylation with 1,2-C2H4Br2 yields [Ru(CO)PMe3(dttd)]. [Ru(PMe3)2dttd] is obtained from [Ru(PMe3)4Cl2] and Li2-dttd, the synthesis of which is also described. In [Ru(PMe3)2(dttd)] the PMe3 ligands are inert, but in [Ru(PØ3)2(dttd)] one PØ3 ligand is easily substituted by CO or N2H4 yielding [Ru(CO)(PØ3)dttd] or [Ru(N2H4)(PØ3)dttd] respectively; [Ru(PØ3)2(dttd)] is obtained from [RU(PØ3)3Cl2] and H2-dttd. The complexes are characterized by elemental analyses, IR, 1H NMR and mass spectroscopy.
Diazadiphosphetidin- Platin (0) - Komplexe/Diazadiphosphetidine Platinum(0) Complexes
Authors: Scherer Otto J. , Krieger Klaus-Dieter 
Published: February 2015

Abstract
The reaction of Pt(COD)2 with cis-[RPNCR3]2 (1), R = CH3, affords the two-coordinate platinum(0) complex PtL2 (2) (L = diazadiphosphetidine 1). In benzene solution PtL2, Pt2L3 (3) and L are in equilibrium. 2 and diphenylacetylene or fumaric acid dinitrile give the platinum diazadiphosphetidine complexes L2Pt(PhCCPh) (4) and L2Pt[H(NC)CC(CN)H] (5), L = 1.
Metall-Schwefeldioxid -Komplexe/ Metal Sulfur Dioxide Complexes
Authors: Hoppenheit Reinhard , Isenberg Wilhelm , Mews Rüdiger 
Published: February 2015

Abstract
The preparation of sulfur dioxide complexes M(SO2)2(AsFe) (1 a-1 g M = Mn, Fe, Co, Ni, Cu, Zn, Mg) is possible in liquid SO2 (a) by oxidation of the metals with AsF5, (b) by metathesis of metal halides, e.g. NiBro, with AgAsF6, (c) by the reaction of metal fluorides, e.g. ZNF2, with AsF5. The spectroscopic properties of these complexes are discussed and the structure of [Mg(SO2)2(AsF6)2]n (1 g) is reported.
Die Kristallstrukturen von PPh4[SnCl3] und PPh4[SnBr3]/ The Crystal Structures of PPh4[SnCl3] and PPh4[SnBr3]
Authors: Müller Ulrich , Mronga Norbert , Schumacher Christina , Dehnicke Kurt 
Published: February 2015

Abstract
PPh4[SnCl3] and PPh4[SnBr3] were prepared by reaction of PPh4X with SnX2 in CH2X2 solutions (X - Cl, Br). The vibrational spectra of the [SnX3]⊖ ions show three SnX3 stretching frequencies, which is caused by deviations from the ideal C3v symmetry. In the crystal structure determinations these deviations show up by slightly different Sn-X bond lengths which are explained by differing hydrogen bridges to phenyl-H atoms. The isotypic crystal structures of both compounds were determined and refined from X-ray diffraction data (R values: 0.042 and 0.034). Although triclinic (space group P1̄), the structures are closely related to the tetragonal AsPh4[RuNCl4] structure type. Very pure SnBr2 is prepared by the reaction of PPh4[SnBr3] with AlBr3 in CH2Br2 solution.
Darstellung und Kristallstruktur von Kupfer(I)tetrachloroaIuminat, CUAlCl4/ Preparation and Crystal Structure of Copper(I) Tetrachloroaluminate, CuAlCl4
Authors: Hildebrandt Kerstin , Jones Peter G. , Schwarzmann Einhard , Sheldrick George M. 
Published: February 2015

Abstract
Crystalline CuAlCl4 was prepared from CuCl and AlCl3 in a quartz tube at 533 K. The crystal structure was determined [P4̄2c, a = 543.0(1), c = 1009.6(1) pm, Z = 2, Rw =0.034 for 345 reflections]. The chlorine atoms form a distorted cubic close-packed lattice, with copper and aluminium each occupying an eighth of the tetrahedral holes (site symmetries 4̄ and 222, respectively).
Schwefel-Stickstoff-Verbindungen, XI. Elektrochemische Untersuchung einiger aromatisch substituierter Schwefeldiimide/ Sulfur-Nitrogen Compounds, XI. Electrochemical Investigations on Some Aromatic Substituted Sulfurdiimides
Authors: Brands Gilbert , Golloch Alfred 
Published: February 2015

Abstract
The electrochemical reduction and oxidation of sulfurdiimines R1-NSN-R2 (R1,2 = C6H5, C6F5, C6H5S, C6F5S) in organic solvents is studied. Both reactions proceed in the sulfur-nitrogen system in a one-electron step. The influences of the substituents are, however, different.
Metallkomplexe mit Tetrapyrrol-Liganden, XXVIII. Mononukleare Nitridomangan(V)-Porphyrine: die ersten Mangan-Stickstoff-Dreifachbindungen/ Metal Complexes with Tetrapyrrole Ligands, XXVIII. Mononuclear Nitridomanganese(V) Porphyrins: the First Manganese Nitrogen Triple Bonds
Authors: Buchler Johann W. , Dreher Christine , Lay Kiong Lam 
Published: February 2015

Abstract
The first complexes containing a manganese-nitrogen triple bond, nitrido(octaethylporphinato) manganese(V) [MnN(OEP)]** and nitrido[meso-tetra(p-tolyl)porphinato]manganese( V) [MnN(TTP)], are prepared by hypochlorite oxidation of the corresponding methoxomanganese( III) porphyrins, Mn(OEP)OMe and Mn(TTP)OMe, in the presence of ammonia. The red, pentacoordinated, diamagnetic species are identified by UV/VIS-, IR-, 1H NMR, and mass spectra. While the isoelectronic oxochromium(IV) or oxomolybdenum( IV) porphyrins behave as weak oxidants or reductants, respectively, the nitridomanganese( V) unit in the square pyramidal environment is chemically remarkably stable.
Studien zum Vorgang der Wasserstoffübertragung, 63. Elektrochemische Herstellung einiger Amalgame und Bestimmung ihrer Potentiale/ Studies on the Occurrence of Hydrogen Transfer, 63. Electrochemical Preparation of Some Amalgams and Measurement of the Potentials
Authors: Horner Leopold , Schmitt Rolf-Erhard 
Published: February 2015

Abstract
The amalgams of lithium, sodium, potassium, barium and zinc were prepared electrochemically (potentiostatic and galvanostatic, see Tables I and II). The potentials of these were measured in acetonitrile, THF and DMF, using the corresponding Perchlorate (Li, Na, K, Ba, Zn) or tetrabutylammonium perchlorate as electrolyte and a standard calomel olektrode (SCE) (Table III). In the case of the lithium amalgam, the dependence of the potential on the lithium content was studied (Table IV). The potential moves slightly to more positive values on dilution, dilution by a factor of 100 producing a shift of only ca. 100 mV.
Eliminierung von Aceton und Bildung von protoniertem Aceton bei der chemischen Ionisation von [2.2.6.6]-Tetramethylcyclohexanon/ Elimination of Acetone and Formation of Protonated Acetone from [2,2,6,6]-Tetramethylcyclohexanone under the Condition of Chemical Ionisation
Authors: Wolfschütz Roland , Franke Wilfried , Heinrich Nikolaus , Schwarz Helmut , Blum Wolfgang , Richter Wilhelm J. 
Published: February 2015

Abstract
By means of appropriately D and 13C labelled precursors it is shown that the proton catalysed degradation of [2,2,6,6]-tetramethyl cyclohexanone {e.g. elimination of acetone and formation of protonatecl acetone from [MH]+) proceeds via two distinct pathways. The energetically favoured one (pathway A, Scheme 1) involves a sequence of [1,2]-methyl migration, ring contraction and methyl migration, whereas the energetically less attractive path B commences with a Wagner-Meerwein ring contraction, followed by hydroxyl and methyl migration. Semi-empirical quantum mechanical calculations (MNDO) are em-ployed to explore computationally relevant parts of the potential energy surface. The syntheses of the specifically 13C labelled title compounds (1 a, b) are described in detail.
Additionsverbindungen von Methylhalogensiianen und Pyridin bei tiefen Temperaturen/ Addition Compounds of Methylhalogenosilanes and Pyridine at Low Temperatures
Authors: Hensen Karl , Busch Reiner 
Published: February 2015

Abstract
By analyzing the melting point diagrams of some methylhalogenosilane-pyridine systems the existance of the stable addition compounds CH3SiCl3 · 2 py, CH3SiBr3 · 2 py, (CH3)2SiBr2 · py, (CH3)3SiBr · py was proved. In the systems (CH3)2SiCl2/py and (CH3)2SiBr2/py unstable 1:2-complexes are also found. (CH3)3SiCl forms no complexes with pyridine.
Phosphonyl- und Phosphinyl-triazene. Elektrophile Substitutionsreaktionen mit Benzol/ Phosphonyl- and Phosphinyl-triazenes. Electrophilic Substitution Reactions with Benzene
Authors: Kreher Richard , Halpaap Reinhard 
Published: February 2015

Abstract
The reaction of phosphonyltriazenes with benzene in the presence of aluminiumchloride is involved with the elimination of nitrogen and followed by electrophilic substitution of benzene. The arylation reaction obviously proceeds via the intermediate formation of arene diazonium ions. Phosphinyltriazenes display the same chemical behaviour.
Die Kristall- und Molekülstruktur von Tris(dimethylamino)boran / The Crystal and Molecular Structure of Tris(dimethylamino)borane
Authors: Schmid Günter , Boese Roland , Bläser Dieter 
Published: February 2015

Abstract
Tris(dimethylamino)borane, X-ray The crystal and molecular structure of tris(dimethylamino)borane, a liquid at room temperature, has been determined by single-crystal X-ray diffraction methods at - 116°C. The single-crystal growth was accomplished by means of a miniature zone melting process on the diffractometer. The structure data are compared with those of other aminoboranes.
Effects of Through-Conjugation on the Molecular Structure of p-Nitroaniline [1]
Authors: Colapietro Marcello , Domenicano Aldo , Marciante Clara , Portalone Gustavo 
Published: February 2015

Abstract
A new X-ray diffraction study of p-nitroaniline shows that through-conjugation has highly significant effects on the geometry of the molecule, as compared to aniline and p-nitrobenzoic acid. The effects include a moderate decrease of the internal angles of the ring at substituted carbons, with respect to values derived by superimposing independent angular distortions from each substituent.
Röntgenstrukturbestimmung von AlCl3-Pyridin-Addukten: Der strukturelle Aufbau im trans-Dichlorotetrakis(pyridin)aluminium(III)- Tetrachloroaluminat(III) und im Trichlorotris(pyridin)aluminium(III) / X-ray Diffraction Study of AICl3-Pyridine Adducts: The Crystal Structure of trans-Dichlorotetrakis(pyridine)aluminium(III)tetrachloroaluminat(III) and of Trichlorotris(pyridine)aluminium(III)
Authors: Pullmann Peter , Hensen Karl , Bats Jan W. 
Published: February 2015

Abstract
Crystals of [Al(C5H5N)4Cl2][AlCl4] are orthorhombic, Pna21, Z = 4, a = 18.522(7), b = 15.141(5), c = 9.593(3) Å, V = 2690(2) Å3 , Dc = 1.440 g/cm3 . The structure has been solved from 5968 diffractometer measured intensities and refined by full-matrix least squares to Rw(F) = 0.032. The crystal structure shows the complex to be trans-dichloro-tetrakis(pyridine)aluminium(III) tetrachloroaluminat(III). The mean trans Al-Cl-and trans Al-N-distances in the octahedron are 2.279(3) and 2.070(4) Å, respectively. Crystals of Al(C5H5N)3Cl3 are monoclinic, P21/c, Z = 4, a = 7.261(2), b = 29.961(4), c = 8.624(1) Å, β = 98.12(2)°, V -1857(1) Å3 , DC = 1.326 g/cm3 . The structure has been solved from 4707 diffractometer measured intensities and refined to Rw(F) = 0.028. The crystal structure shows octahedral complexes AlCl3·3 (C5H5N) with trans geometry. The Al-N-distance trans to chlorine (2.096(2) Å) is significantly longer than the two other Al-N-distances (mean 2.072(2) Å).
Darstellung und Struktur von Dimesitylzinnoxid / Synthesis and Structure of Dimesityltinoxide
Authors: Weber U. , Pauls N. , Winter W. , Stegmann H. B. 
Published: February 2015

Abstract
Trimesityltin bromide reacts with concentrated aqueous ammonia to give trimesityltin hydroxide. This compound eliminates mesitylen and yields dimesityltin oxide. The product was investigated bv 13C NMR, mass spectroscopy and X-ray diffractions. Di-mesityltinoxide crystallizes in the space group P21/w with a = 25.38(1) Å, b = 12.525(5) Å, c= 32.91(1) Å, β= 91.37(3)° and two molecules in the asymmetric unit (Z=8). The R-factor is 0.049 for 4688 symmetry-independent reflections. The trimeric molecules have six-membered tin-oxygen heterocycles in a twist conformation.
Cyclopropyl- und Alkyl-Carbanionen mit Akzeptor-Substituenten in α-Stellung. Eine MO-Studie zur Konfiguration der Anionen und Acidität der entsprechenden CH-Säuren / Cyclopropyl and Alkyl Carbanions with Acceptor Substituents in α-Position. An MO Study of the Configuration of the Anions and the Acidity of the Corresponding CH Acids
Authors: Wagner Hans-Ulrich , Boche Gemot 
Published: February 2015

Abstract
a-Hydrogens a-Hydrogens of R-C ≡ C-and N ≡ C-substituted cyclopropanes are more acidic than their open chain analogs, as expected from the higher acidity of cyclopropane versus propane. In the case of the carbonyl substituted species, however, this order is reversed. Furthermore, in H/D exchange reactions of optically active compounds, only cyclopropyl cyanides retain their configuration; aliphatic and cyclopropyl ketones exchange and racemize essentually at the same rate.
This behaviour has been rationalized qualitatively in the following manner: RC = C-and N ≡ C-substituents stabilize a negative charge mostly inductively; on the other hand, with carbonyl groups, delocalisation of the negative charge (resonance) is more important than the inductive effect. Thus the unfavourable configuration (I-strain) of the planar cyclopropyl enolate anions is in agreement both with the low acidity of the corresponding cyclopropanes and with the loss of optical activity in H/D-exchange reactions.
In order to put this explanation on a more quantitative basis, we calculated the relative proton affinities of isopropyl-and cyclopropyl-carbanions by means of the ab-initio STO-3G method. In the case of X = H, CF3 and C ≡ N, the cyclic anion (CH2)2C⊖X is more stabilized by the substituent X than in the anion (CH3)2C⊖X; with X = CHO, COOH and NO2 the order is reversed. Cyclopropyl anions should have a pyramidal configuration with X = H, CF3, C ≡ N and NO2, which indicates a strong inductive effect also of the nitro group.
In summary: STO-3G calculations support the qualitative explanations of the experimental results with regard to the acidities of substituted cyclopropanes.
Alkaloide aus Catharanthus roseus-Zellkulturen, III [1] / Alkaloids from Catharanthus roseus Tissue Cultures, III [1]
Authors: Kohl Werner , Witte Barbara , Höfle Gerhard 
Published: February 2015

Abstract
From the methanol extract of Catharanthus roseus tissue cultures sitsirikine (2), isositsirikine (3), dihydrositsirikine (4), yohimbine (5), 3-iso-19-epiajmalicine (6), pleio-carpamine (7), antirhin (8) and two up to now unknown alkaloids have been isolated in addition to the compounds previously found in the hexane extract. The structures belonging to lieteroyohimbane, vallesiachotamine, corynanthe and related types were deduced by UV, NMR and mass spectroscopy.
Die Kristallstruktur von Hexa-μ-chloro-μ4- oxo - tetrakis [hexamethy lentetramin - kupfer(II)] , [CU4Cl60(C6H12N4)4] , einem Kupfer(II)-Komplex mit Berylliumoxoacetat-ähnlicher Struktur / The Crystal Structure of Hexa-μ-chloro-μ4- oxo-tetrakis [hexamethylenetetraminecopper- (II)], [Cu4Cl6O(C6H12N4)4], a Copper(II) Complex with a Structure Related to that of Beryllium Oxoacetate
Authors: Pickardt Joachim , Rautenberg Norbert 
Published: February 2015

Abstract
By reaction of solutions of CuCl2·2H2O and hexamethylenetetramine, C6H12N4, in acetone, a complex [Cu4Cl6O(C6H12N4)] could be obtained as single crystals. An X-ray analysis shows that the complex has a structure related to that of basic beryllium acetate. An oxygen atom is tetrahedrally surrounded by four cop-per atoms which, together with six chlorine atoms, form an adamantane-like core. Each copper atom is bonded via a nitrogen atom to a hexamethylenetetramine molecule.
Zur Darstellung und Kristallstruktur von β-NbO2 / Synthesis and Crystal Structure of β-NbO2
Authors: Schweizer H.-J. , Gruehn Reginald 
Published: February 2015

By using chemical transport reactions with various transporting agents (HgCl2, NbCl5, Nb3O7Cl) a slightly substoiehiometric NbO2-phase, β-NbO2, was obtained from samples with O/Nb ∼ 1.5 (source; T > 1373 K) and with deposition temperatures > 1273 K (sink). The rango of composition of β-NbO2 was found to exist from NbO1.990 to NbO1.998.
The structure of the tetragonal, column-shaped black crystals was determined by X-ray diffraction. It crystallizes tetragonally in the space group I41 with lattice constants a = 9.693(3) Å, c = 5.985(1) Å and Z = 10 formula units.
The crystal structure of β-NbO2 is shown to be a deformed rutile type. As in α-NbO2 the Nb-atoms are grouped in pairs. However, both oxides are different with respect to their long-range order.
Kristallstrukturell von Verbindungen A2X2 (A=S, Se; X=Cl, Br) / Crystal Structures of Compounds A2X2 (A=S, Se; X=Cl, Br)
Authors: Kniep Rüdiger , Körte Lutz , Mootz Dietrich 
Published: February 2015

Abstract
The crystal structures of compounds A2X2 (A=S, Se; X=Cl, Br) contain molecules X-A-A-X with dihedral angles between 83.9° and 87.4°. Three different types of molecular packing are realized: S2CI2, S2Br2 (α-Se2Br2) and β-Se2Br2(Se2Cl2). Details of molecular geometries as well as crystal structures are discussed.
Derivatives of NPCl2NSOCl)2 and (NPCl2)2NSOCl, Part XXI [1]. The Synthesis of a Spiro Phosphazene Derivative of NPCl2(NSOPh)2
Authors: Winter Herman , Grampel Johan C. van de 
Published: February 2015

Abstract
The preparation of the spirocyclic compounds cis-and trans-NP[(NPCl2)2NCH3](NSOPh)2 from cis-and trans-NPCl2(NSOPh)2 is described as well as the synthesis of the inter-mediates. The 31P NMR data are discussed.
Darstellung und Kristallstruktur von Di-gold(III)bis(selenit)oxid, Au2(SeO3)2O / Preparation and Crystal Structure of Di-gold(III) Bis(selenite) Oxide, Au2(SeO3)2O
Authors: Jones Peter G. , Sheldrick George M. , Schwarzmann Einhard , Vielmäder Andreas 
Published: February 2015

Abstract
Au2(SeO2)2O was prepared from gold and excess selenic acid in a sealed tube at 533 K. The crystal structure [Pba2, a = 659.2(2), b = 1183.7(3), c = 399.8(1) pm, Z = 2,R = 0.087] was determined; gold atoms are bridged by oxide ions (lying on twofold axes) and selenite ions. The extended structure consists of polymeric layers parallel to the xy-plane. The light atom positions are inaccurate because of the presence of a heavy atom in a polar space group.
Monomere und dimere Oxotrihalogenoselenate(IV): Darstellung, Struktur und Eigenschaften von [As(C6H5)4]SeOCl3 und [N(C2H5)4]SeOCl3 / Monomerie and Dimeric Oxotrihalogenoselenates(IV): Preparation, Structure and Properties of [As(C6H5)4]SeOCl3 and [N(C2H5)4]SeOCl3
Authors: Krebs Bernt , Hucke Marita , Hein Michael , Schäffer Andreas 
Published: February 2015

Abstract
The monomeric SeOCl3- ion, which can be prepared as the tetraphenylarsonium salt from SeOCl2 and As(C6H5)4Cl, was structurally characterized by a low-temperature single crystal X-ray diffraction analysis. [As(C6H5)4]SeOCl3 is monoclinic, space group P21/c, with a = 9,332(3), b = 13,761(4), c = 18,985(6) Å, β = 110,97(3)° (at -135 °C), Z = 4; it contains a novel type of ψ-trigonal bipyramidal oxotrichloroselenate(IV) anion which is not associated to dimers or polymer chains as in known structures. The equatorial positions are occupied by doubly bonded oxygen (Se-O 1,601(3) Å) and by one Cl(Se-Cl 2,234(1) Å), the axial Se-Cl bonds (2,430(1) and 2,475(1) Å) being significantly longer. [N(C2H5)4]SeOCl3, which was obtained as crystals by oxidation of trichloroselenate(II), is triclinic, space group P1̄, with a = 10,607(3), b = 8,950(2), c = 8,862(2) Å, α = 119,79(2)°, β = 101,07(2)°, γ = 96,28(2)°, Z = 2. The X-ray structure analysis shows the anions to be present as centrosymmetric dimers Se2O2Cl6
2- like in the [P(C6H5)4]+ salt, with two tetragonal SeOCl4 pyramids linked through a Cl···Cl edge and the lone pairs trans to the axial Se-O bonds (1,589(4) Å). Se-Cl bond lengths are 2.270(1) and 2,351(2) Å (terminal); 2,698(1) and 2,920(1) Å (bridging). The results show that the nature of the reaction products of the Lewis acid SeOCl2 with halogenides as bases changes very sensitively with small variations in cations and environment. The vibrational spectra are discussed.