bluuebunny/crossref_metadata_2025 huggingface dataset:
Darstellung und Kristallstrukturen von [Ph4As+][PS2(N3)2] und [(n-C3H7)4N+]2[(NCPS2)2S2-]/ Preparation and Crystal Structures of [Ph4As+][PS2(N3)2
–] and [(n-C3H7)4N+]2 [(NCPS2)2S2
–]
Authors: Roesky Herbert W. , Noltemeyer Mathias , Sheldrick George M.
Published: March 2015

The diazidodithiophosphate anion [PS2(N3)2
-] can be isolated with a large cation as (Ph4As+][PS2(N3)2
-] (1). [PS2(N3)2
-] is formed by the reaction of P4S10 with NaN3 in acetonitrile as a solvent. [(NCPS2)2S2
-] results from the reaction of P4S10 with NaCN in acetonitrile and is isolated as [(n-C3H7)4N+H(NCPS2)2S2-] (2). 1 crystallizes in the triclinic space group P1̄ with a - 1329.3(3), b = 1419.1(3),c = 2182.3(5) pm, α = 71.71(2), β = 87.21(2), γ = 84.97(2)° and Z = 6. Crystals of 2 are monoclinic, space group P21/n, a - 1899.0(3), b - 949.0(2), c = 2128.4(5) pm, β = 112.90(2)°, Z = 4.
Kurze inter-und intramolekulare W asserstoffbrückenbindungen in sauren Salzen halogensubstituierter Orthophthalsäuren/ Short Inter-and Intramolecular Hydrogen Bonds in Acid Salts of Halogen-Substituted o-Phthalic Acids
Authors: Mattes Rainer , Dorau Angela
Published: March 2015

The hydrogen bonding in several acid salts of 4,5-dichlorophthalic, 3,6-dichlorophthalic and 3-fluorophthalic acid have been studied by IR spectroscopy and X-ray structure analysis. NH4H [3,6-Cl2C8H2O4] and KH[3-FC8H3O4], with O···O distances of 247 and 254.1(4) pm, respectively, belong to Speakman’s type B2 of acid salts of dicarboxylic acids. In NH4H[4,5-Cl2C8H2O4] · H2O a short hydrogen bond of 253(1) pm is formed to the H2O molecule. A very short intramolecular hydrogen bond of only 234.0(10) pm length was found in N(C4H9)4H[4,5-Cl2C8H2O4], In the [3,6-Cl2C8H2O4]2- dianion both carboxylate groups are nearly orthogonal to the phenyl ring.
Beiträge zur Chemie der Carbonylkomplexe mit Germanium-bzw. Zinn-Übergangsmetall-Bindungen/ Contributions to the Chemistry of Carbonyl Complexes with Germanium or Tin Transition Metal Bonds
Authors: Behrens Helmut , Moll Matthias , Merbach Peter , Trümmer Karl-Heinz
Published: March 2015

Dihalogeno bis(carbonylm etalato) germanium (IV) and tin(IV ) com pounds listed in Table I are obtained in high yields by the reaction o f TlCo(CO)4 or TlFe(CO)3NO with trihalogeno carbonylmetalato germanium(IV) and tin(IV) complexes. The new com pounds are characterized by their analyses, mass and vibrational spectra.
Darstellung und Schwingungsspektren von Fluoro-Chloro-Osmaten(V)/ Preparation and Vibrational Spectra of Fluoro-Chloro-Osm ates(V)
Authors: Preetz W. , Groth Th.
Published: March 2015

By oxidation of the pure fluoro-chloro-osmates(IV ) with BrF3 in dichlorom ethane the mixed pentavalent complexes [OsF5Cl]-, cis-[OsF4Cl2]-, fac-[OsF3Cl3]- and cis-[OsF2Cl4]- are formed without replacement of ligands. Trans-[OsF4Cl2]- and trans-[OsF2Cl4]- are generated from the corresponding osmates(IV) by oxidation with PbO2 in dichloromethane under addition of trifluoroacetic acid. The vibrational spectra o f the mixed ligand complexes are assigned according to point groups D4h, C4v, C3v and C2v. The increased bond strength com pared with the corresponding Os(IV ) complexes is indicated by a significant shift to higher energy by about 5 -15% . The Os -Cl stretching vibration of [OsF5Cl]- and also the symmetric ClOsCl of trans-[OsF4Cl2]- is split by the isotopes 35Cl and 37Cl, showing two and three well resolved sharp Raman lines in the expected ratio of intensities, respectively.
Synthese und Kristallstruktur des Anions [P4S9N]− / Synthesis and Crystal Structure of the Anion [P4S9N]−
Authors: Roesky Herbert W. , Benmohamed Nasreddine , Noltemeyer Mathias , Sheldrick George M.
Published: March 2015

[(nC3 ,H7)4N]+[P4S4N]− 1 has been synthesized from P4S10 and [(nC3H7)4N]+ [S2P(N3)2]− . 1 crystallizes in the space group P21/c with a = 936.9(2), b = 1731.1(3), c = 1694.6(3) pm , β = 93.41(2)° and Z = 4. The [P4S9N]~ anion has an adamantane-like structure, with bridging rather than terminal nitrogen.
Das Dispiro[5.1.5.1]tetradecan-Gerüst als Baustein für thermotrope Flüssigkristalle / Thermotropic Liquid Crystals Containing the Dispiro[5.1.5.1]tetradecane Unit
Authors: Calaminus W. , Vögtle F. , Eidenschink R.
Published: March 2015

Several 3 .11-disubstituted dispiro[5.1.5.1]tetradecane-7,14-dions were prepared and the cis/trans-isomers were separated. The trans -stereoisomers were converted into the gem-dihalide ketones and mono- and dithioketones. The phase transfer temperatures were determined. Liquid crystal phases were observed.
A New Alkaloid from Root Bark of Capparis decidua
Authors: Ahmad Viqar Uddin , Arif Shoib , Amber Aziz-ur-Rahman , Nasir M. Ajmal , Ghani K. Usman
Published: March 2015

A new spermidine alkaloid, capparisine (1) has been isolated from the alcoholic extract of the root bark of Capparis decidua, and its structure was elucidated by spectral studies.
Assignment of 31P Chemical Shifts to Isomers of 2,3-Dialkoxy-λ3-diazadiphosphetidines — Crystal and Molecular Structure of trans-[PhNP(OCH2CF3)]2
Authors: Kumaravel S. S. , Krishnamurthy S. S.
Published: March 2015

Geometrical isomers of λ3-diazadiphosphetidines show large differences in their 31P chemical shifts. Trifluoroethoxylation of cis-(PhNPCl)2 gives only the 'low-field' isomer initially, for which the crystal structure is determined. The compound crystallises in the triclinic space group P1̄ with a = 9 .6 2 4 (4 ).6 = 10.107(4),c = 11.140(7) Å ; a = 105.65(4),β = 110.59(4),y = 93.82(3)°;and Z = 2. The structure was solved by direct methods and refined to R = 0.045. The alkoxy groups are trans to each other. On standing in solution. trans -[PhNP(OCH2CF3)]2 transforms slowly and almost completely into its cis analogue with a high field 31P chemical shift
Alkoxistannate, II [1] Tri(tert-butoxi)alkalistannate(II): Darstellung und Strukturen / Alkoxistannate, II [1] Tri(tert-butoxi)alkalistannates(II): Synthesis and Structures
Authors: Veith M. , Rosier R.
Published: March 2015

Tri(tert-butoxi)alkalistannates (M(O'Bu)3Sn, M = Li, Na, K, Rb, Cs) are obtained by reaction of alkali-fert-butanolates with tindi-tert-butoxide. If M equals Li or Na (1, 2) molecular com pounds are formed, which consist of two formula units. 1 crystallizes in a m onoclinic cell (space group P21/c; a = 966.5(3), b = 1819(1), c = 1014(1) pm. β = 107.1(1)°, Z = 4); 2 is triclinic (space group P1̄; a = 1041(1), b = 2046(1), c = 1033(1) pm. a = 92.3(2), β = 118.6(1), y = 108.3(3)° and Z = 4). The molecules 1 and 2 are closely related structurally despite their different space groups. The common structural feature is a Sn2O6M2 cage, which is built of two seco-norcubane Sn2M2O , units, sharing a M2O2 four-membered ring. Characteristic distances are: 1: Sn-O = 209.3, L i-O = 193.0 and 211.6 pm, 2: Sn-O = 210.5, Na-O = 227.4 and 240.7 pm. The tert/-butoxistannates of K, Rb and Cs (3, 4, 5) all crystallize in the orthorhombic crystal system, space group P212121 (cell constants of 3: a = 1907(1), b - 1060(1), c - 896(1) pm, Z = 4). Contrary to the lithium- and sodium derivates 3, 4 and 5 have a polymeric structure. The one dimensional polymer consists of distorted trigonal bipyramidal SnO3M “cages” (substituted at the oxygen atoms by tertbutyl groups), which align in a way to allow the metal atom to have a five-fold oxygen coordination. The tin atoms have trigonal pyramidal coordination. While the tin-oxygen bond lengths are essentially invariant (average value 206.7 pm ), the potassium-oxygen distances range from 256.4(5) pm to 318.8(6) pm
Synthese, Molekül- und Kristallstruktur von 3-(2,6-Dimethylphenylamino)-4,5-diethyl-1,2,3-diselenaborol / Synthesis, Molecular and Crystal Structure of 3-(2,6-Dimethylphenylamino)-4,5-diethyl-1,2,3-diselenaborole
Authors: Habben Carl , Meller Anton , Noltemeyer Mathias , Sheldrick George M.
Published: March 2015

The title com pound, isolated from the reaction of 3-iodo-4,5-diethyl-1,2,3-diselenaborol with N-lithio-2,6-dim ethylaniline, crystallizes in space group C 2/c with a = 1511.8(3) pm, b = 901.6(2) pm, c = 2444.4(6) pm, and β = 104.17(2)°. Refinement converged to R = 0.042 for 1555 observed unique reflections. 1H, 11B , 13C, 14N, 77Se NMR and MS data are also reported, and the results are compared with those o f the sulfur analog
The Molecular Structure of 4-Methyl Benzenesulfonyl Chloride
Authors: Rigotti G. , Rivero B. E. , Filgueira R. R.
Published: March 2015

The m olecular structure of C7H7SO2Cl was determined by X-ray diffraction and refined to R = 0.060 and Rw = 0.053 from 1170 unique reflections. The unit cell is triclinic, P1̄ , with Z = 2, a = 8.528(5), b = 8.214(3), c = 6.306(2) A; a = 95.47(3), β = 104.41(3), γ = 93.08(4)°; V = 424.6(3) Å3; ju = 6.30 cm-1; δcalc = 1.49 M g-m-3; F(000) = 196.

The dihedral angle between the benzene ring and the Cl - S - C (1) plane [84.3(1)°] is similar to those observed for benzenesulfonyl chlorides where molecular packing results from normal van der Waals interactions [1, 2], The compound has normal bond lengths and angles. Distortion of the benzene ring is in agreement with the predicted a- and π-effects of substituent groups [3], No significantly short intermolecular distances were found
Imidazolkatalysierte Ringerweiterung von 2-(Diarylmethyl)- und 2-(ArylaIkyI)-1,2-oxazetidin-3-onen zu 4-Oxazolidinonen / Imidazole-Catalyzed Ring Expansion of 2-(DiaryIm ethyl)- and 2-(Arylalkyl)-1,2-oxazetidin-3-ones to 4-Oxazolidinones
Authors: Lauterbach Thomas , Geffken Detlef
Published: March 2015

The imidazole-catalyzed ring expansion of 2-(diarylmethyl)- and 2-(arylalkyl)-1,2-oxazetidin- 3-ones 2, easily obtained from the corresponding glycolohydroxamic acids 5, produces 4-oxazolidinones 4 in high yields. In most cases the reaction can be carried out by reacting the hydroxamic acids 5 with 1, 1'-carbonyldiim idazole. Compounds 4a and 4f arise by thermolytic fragmentation of the corresponding perhydro-1,5,2-dioxazinan-3,6-diones 1a, d.
S5N5[SnCl5(CH3CN)]; Synthese, IR-Spektrum, 119Sn-Mößbauer-Spektrum und Kristallstruktur / S5N5[SnCl5(CH3CN)]; Synthesis, IR Spectrum , Mössbauer Spectrum and Crystal Structure
Authors: Patt-Siebel Ute , Ruangsuttinarupap Somluck , Müller Ulrich , Pebler Jürgen , Dehnicke Kurt
Published: March 2015

S5N5[SnCl5(CH3CN)] is prepared by the reaction of SnCl2 with trithiazyl chloride in acetonitrile suspension. The compound is characterized by its IR spectrum, the 119Sn Mössbauer spectrum and by an X-ray crystal structure determination (1851 observed, independent reflexions, R = 0.024). S5N5[SnCl5(CH3CN)] crystallizes in the monoclinic space group P21/n with Z = 4 and the lattice dimensions a = 758.8; b = 1574.6; c = 1429.1 pm; β = 97.65°. The compound consists of planar S5N5
® cations with the azulene-like structure, and anions [SnCl5(CH3CN)]e in which the tin atom has a distorted octahedral coordination. The bond angle Sn-N ≡ C (168°) is surprisingly small.
Die Spektren und Kristallstrukturen der Addukte CI5Sb · [N(i-C3H7)CN(i-C3H7)] und Cl4Sn · 2 [N(i-C3H7)CN(i-C3H7)] / Spectra and Crystal Structures of the Adducts Cl5Sb · [N(i-C3H7)CN(i-C3H7)] and Cl4Sn · 2 [N(i-C3H7)CN(i-C3H7)]
Authors: Hausen H.-D. , Schwarz W. , Rajca G . , Weidlein J.
Published: March 2015

Spectra and Crystal Structures of the Adducts C l5Sb • [N(/-C3H 7)C N (i-C3H 7)] and C l4Sn • 2 [N(/-C3H 7)CN(/-C3H 7)j X-Ray, Vibrational Data, Diisopropylcarbodiimide Adducts of SbCl5, SnCl4 Thecarbodiimide adducts Cl5Sb <-(—N (R) = C = N R)(1) and Cl4S n ^ (-N (R) = C = N R) 2(2)(R = /-C3H 7) have been prepared by the reaction o f R —N = C —N — R with SbCl5 in a 1:1 and with SnCl4 in a 2:1 molar ratio, respectively. The vibrational spectra (IR and Raman) of both compounds have been regarded and assigned to the skeleton modes. The X-ray structure determination shows the orthorhombic space group Pna2, with 4 formula units per unit cell for 1. Adduct 2 has a trans-configuration and crystallizes in the triclinic space group P 1 with only one molecule per unit cell.
Oxidation of Imines by Selenium Dioxide
Authors: Martin Hubert , Herrmann Rudolf
Published: March 2015

The oxidation of imines containing a α-methylene group by selenium dioxide is investigated. The products are shown to be a-imino carbonyl compounds by spectroscopic methods. The reactivity of various imines is discussed.
Darstellung und Reaktionen von 1,3-Benzdioxol-biscarbaldehyden. Ein Beitrag zur Strukturaufklärung des Nepenthons A / Synthesis and Reactions of 1,3-Benzodioxoledicarboxaldehydes. A Contribution to the Structure Elucidation of Nepenthone-A
Authors: Daliacker Franz , Schieuter Hans-Joachim , Schneider Petra
Published: March 2015

We describe the preparation o f 1,3-Benzodioxole-5,6-dicarboxaldehyde (1d) and 1,3-Benzdioxole- 4,5-dicarboxaldehyde (3h). Under especially mild conditions also the synthesis of 4,7- Dimethoxy-1,3-benzodioxole-5,6-dicarboxaldehyde (4g) can be achieved. Its reaction with Hydroxyacetone leads to quinone 9a, which after methylation can be identified with the dim ethylether of Nepenthone-A .
Uber die Wellenlängen-Abhängigkeit der Photo-Eliminierung des Biphenyl-Systems aus cis-Bis(phenyl)platin(II)-Verbindungen / On the Wavelength Dependence of the Photoelimination of the Biphenyl System from cis -Bis(phenyl)platinum (II) Compounds
Authors: Brune Hans Albert , Mayr Ulrike , Schmidtberg Günther
Published: March 2015

Excitation of the compounds cis -{Pt[P(n-C4H9)3]2(4-XC6H4)2} with radiation o f the wavelengths 287.5 and 312.0 nm resulted in the reductive elimination of the substituted biphenyls 4-XC6H4-C6H4X-(4) (X=CF3,CH3,C(CH3)3,OCH3), whereas they are photostable towards irradiation of 253.5 nm. It is demonstrated that the elimination is a regiospecific pericyclic reaction at platinum; no free radicals are involved.
Reactions with Aziridines, 37 [1]. N,N'-Substituted 1,1-Dimethylethylenediamines by Highly Regioselective Ring Opening of Activated 2,2-Dimethylaziridines through Aliphatic Amines
Authors: Buchholz Berthold , Onistschenko Andreas , Stamm Helmut
Published: March 2015

Secondary and primary aliphatic amines 2 form regioselectively N,N '-substituted 1,1-dimethylethylenediamines by reaction with activated 2,2-dimethylaziridines 1. The kind of activation (X in 1), determines the mode of ring opening: X = sulfonyl gives structure 3, X = acyl or 2,4- dinitrophenyl structure 4.
Darstellung und Kristallstruktur von Palladiumoxidchlorid Pd2OCl2/Preparation and Crystal Structure of Palladium Oxide Chloride Pd2OCl2
Authors: Dannecker Beate , Thiele Gerhard
Published: March 2015

Pd2OCl2 was obtained by reaction of γ-PdCl2 and PdO·nH2O in a KNO3/NaNO3 melt at 450 °C. Single crystals were grown from a TlCl flux. The crystal structure of the tetragonal compound (a = 631.3(2) pm, c = 987.2(2) pm, space group I41 /amd) is built up from bands of edge shared square planar PdO2Cl2 groups connected by common O-atoms to a framework. The relationship between the structures of Pd2OCl2 and PdO is discussed.
Darstellung und Kristallstrukturen von LiGaBr4 und LiGaBr3/Preparation and Crystal Structure of LiGaBr4 and LiGaBr3
Authors: Hönle Wolfgang , Simon Arndt
Published: March 2015

The com pounds LiGaBr4 and LiGaBr3 are prepared by reaction of stoichiometric mixtures of LiBr and GaBr3 or GaBr2, respectively, in glass am poules at 250 °C. Single crystal X-ray studies show LiGaBr4 to be isotypic to LiAlCl4 containing GaBr4 tetrahedra arranged as in the structure of SnBr4 and Li+ ions filling octahedral voids [d̄(GaBr) = 232.5, d̄(Li -Br) = 280.3 pm]. LiGaBr, has to be formulated as Li2[Ga2Br6] and the Ga -Ga-bonded unit Ga2Br6 has an ecliptic confor­mation. The L i+ ions occupy octahedral voids, and the LiBr6 octahedra are linked via apices, [d(Ga -Ga) = 240.4, d̄(Ga -Br) = 238.9, d̄(L i-B r) = 281.1 pm]. The structures is compared with the structures of PuBr3, Re3B, FeB and Ga2I3, and the group-subgroup relationship with GdFeO3 is established.
Darstellung und Molekülstruktur des Ferrocenylkomplexes CpW(NO)2Fc und seine Oxidation zu CpWO2Fc/Synthesis and Molecular Structure of the Ferrocenyl Complex CpW(NO)2Fc and its Oxidation to CpWO2Fc
Authors: Herberhold Max , Kniesel Heidemarie , Haumaier Ludwig , Gieren Alfred , Ruiz-Péreza Catalina
Published: March 2015

The σ-ferrocenyl complex CpW (NO)2Fc (1) was prepared from CpW (NO)2Cl and ferrocenyl lithium, and oxidized by air in CH2Cl2 solution to give CpWO2Fc (2). An X-ray crystal structure analysis of 1 indicated the presence of two almost linear nitrosyl groups (with W -N -O angles of 173.0(9) and 175.4(7)°). The W -C (ferrocenyl) bond length is 2.164(10) Å.
Biflavonoide aus Schinus terebinthifolius Raddi (Anacardiaceae)/ Biflavonoids from Schinus terebinthifolius Raddi (Anacardiaceae)
Authors: Skopp Gisela , Schwenker Gerhard
Published: March 2015

Three biflavonoids together with gallic acid have been isolated for the first time from the drupes of S. terebinthifolius. They have been characterized through chemical and spectral data.
Komplexe mit substituierten 2,5-Dihydroxy-p-benzochinonen: Das isotype Paar BaC6X2O4 · 3 H2O (X = Cl, Br) / Complexes with Substituted 2,5-Dihydroxy-p-benzochinones: The Isotypic Pair BaC6X2O4 · 3 H2O (X = Cl, Br)
Authors: Robl Christian , Weiss Armin
Published: March 2015

BaC6X2O4 · 3H2O (X = Cl, Br) crystallizes in the orthorhombic space group Cmca. 4 of the 8 oxygen atoms around Ba2+ belong to two different dianions, chelating Ba2+. In this way 1-dimensional corrugated chains are formed, interlinked by two oxygen atoms of neighbouring chains, thus forming layers. This interconnection is of polar character within a layer. The in­terlinking oxygen atoms have one carbon- and two Ba2+ neighbours. CN 8 is completed by two water molecules. The latter and a further water molecule situated between the layers may be removed reversibly in a topochemical reaction without destruction of the structure.
Reaktionen von Wolframhexafluorid mit N-Trimethylsilyliminotriphosphoranen — Kristallstruktur von (Me3P = N)2WF4 / Reactions of Tungsten Hexafluoride with N-Trimethylsilyliminotriphosphoranes — Crystal Structure of (Me3P = N)2WF4
Authors: Roesky Herbert W. , Katti Kattesh V. , Seseke Ulrich , Scholz Uwe , Herbst Regine , Egert Ernst , Sheldrick George M.
Published: March 2015

The phosphiniminato-substituted tungsten(VI) fluorides (PhpMe)3P=NWF5 (2), [(PhpMe)3P=N]2WF4 (3), (Me3P=N)2WF4 (4) and [(t-buNH)Ph2P=N]2WF4 (6) have been pre­pared from the corresponding SiMe3 derivatives by reaction with WF6. The starting materials (PhpMe)3P = NSiMe3 (1) and (t-buNH)Ph2P=NSiMe3 (5) are obtained by the reaction of the phosphanes with Me3SiN3. The crystal structure of 4 shows that the cis isomer was formed. Although the molecular geometry of 4 is similar to that of (Ph3P=N)2WF4, some important differences are observed arising from the different electronic properties of the substituents.
Synthesewege zu einfachen Di- und Trisilylmethanen: Potentielle Ausgangsstoffe für die CVD-Abscheidung von amorphem Silicium a-SiC: H / Synthetic Pathways to Simple Di- and Trisilylmethanes: Potential Starting Materials for the CVD Deposition of Amorphous Silicon a-SiC :H
Authors: Schmidbaur Hubert , Ebenhöch Jan
Published: March 2015

Methods for the preparation of simple silaalkanes with a high content of silicon and hydrogen have been explored. Target molecules, like H3SiCH2SiH3 and HC(SiH3)3, may serve as precursor molecules for the production of photovoltaic elements through thermal or discharge (plasma) CVD processes. Among a variety of synthetic pathways, the reactions between HSiCl3 and HCCl3 in the presence of an amine (Benkeser reaction) and the direct synthesis from silicon and polychloromethanes proved most promising for large scale preparations. The CH2X2/KSiH3 metathesis is most useful on the laboratory scale. - The Grignard synthesis was employed for partly methylated homologues, like H3SiCH2SiH2CH3, H3SiCH2SiH(CH3)2, H3SiCH2Si(CH3)3, and related molecules. The magnesium reduction of CHBr3/SiCl4 and CHBr3/CH3SiCl3 mixtures serves best for the preparation of HC(SiCl3)3, which can be converted into HC(SiH3)3 using LiAlH4. Attempts to synthesize tetrasilylmethane via the same route, C(SiH3)4, led only to the formation of HC(SiH3)3.
Übergangsmetallkomplexe mit Schwefelliganden, XXIV* Reduktive Nitrosylierung von [MoCl2(dttd)] zu [Mo(NO)2(dttd)];Eigenschaften, Struktur und Reaktion zu NPR3-Komplexen[Mo(NO)(NPR3)dttd] (PR3=PMe3, PEt3, PMePh2, PEtPh2, PPh3;dttd2-=2,3,8,9-Dibenzo-1,4,7,10-tetrahiadecan(2-)) / Transition Metal Complexes with Sulfur Ligands, XXIV*Reductive Nitrosylation of [MoCl2(dttd)] to [Mo(NO)2(dttd); Properties, Structure an Reaction to NPR3 Complexes [Mo(NO)(NPR3)dttd] (PR3=PMe3, PEt3, PMePh2, PEtPh2, PPh3; dttd2-=2,3,8,9-dibenzo-1,4,7,10-tetrahiadecane (2-))
Authors: Sellmann Dieter , Keller Johannes , Moll Matthias , Beck Horst Philipp , Milius Wolfgang
Published: March 2015

In order to study the properties of sulfur coordinated transition metal centers. [MoCl2dttd] (dttd2 = 2,3,8,9-dibenzo-1,4.7,10-tetrathiadecane(2-)) was reacted with NO in the presence of Zn. [Mo(NO)2dttd] was obtained whose X-ray structure analysis shows that Mo is coordinated pseudo-octahedrally by two trans thiolato S, two cis thioether S as well as two cis N atoms of nearly linear MoNO groups. With respect to its low v(NO) frequencies (1760/1665 cm -1) and quite normal bond lengths as well as angles [Mo(NO)2dttd] shows unexpectedly facile and rapid reactions with nucleophiles; with two equivalents of PR3 (PMe3, PEt3, PMePh2, PEtPh2, PPh3) it yields the corresponding phosphiniminato complexes [Mo(NO)(NPR3)dttd] and free phosphinoxides OPR3, respectively. Reaction mechanisms as well as the bonding situation in the [Mo(NPR3)] entity are discussed; on the basis of 95Mo and 14N NMR it is concluded that the conversion of NO into NPR3 ligands includes a reduction of N(+2) to N(-3) as well as an oxidation of (formal) Mo(+2) to Mo(+3). With H2O the [Mo(NO)(NPR3)dttd] complexes hydro­lyze with loss of the NPR3 ligands and formation of binuclear [Mo(NO)dttd]2. The ease of hydrolysis depends on the substituents R: In THF [Mo(NO)(NPMe3)dttd] hydrolyzes at 20 °C within a few minutes, [Mo(NO)(NPPh3)dttd], however, needs the addition of cone. HCl.
Absorption and Fluorescence Spectra of Bis(porphyrinato)zinc(II) Complexes with a Flexible Polyatomic Chain
Authors: Nishida Yuzo , Okamoto Masaya , Kida Sigeo
Published: March 2015

Relationship between the steric conformation and the efficiency of energy transfer in binuclear zinc(II) porphyrin complexes was interpreted in terms of the absorption and fluorescence spectra.
Wrightiin, a New Chlorinated Depside from Erioderma wrightii Tuck (Ascolichenes)
Authors: Maass Wolfgang S. G. , Hanson Alfred W.
Published: March 2015

The structure of wrightiin, a depside metabolite of Erioderm a wrightii is shown by X-ray crystalo-graphy to be 2. The mass spectrum is anomalous.
Synthesis of 5-AminoIevulinic Acid
Authors: Benedikt Eva , Köst Hans-Peter
Published: March 2015

A 3-step synthesis of 5-aminolevulinic acid is described.
Die Kristallstrukturen von Strontium- und Bariumhexacyanoferrat(III)-Hexamethylentetramin-Hydraten. Strukturmodell für Additionsverbindungen der Alkali- und Erdalkalimetallhexacyanoferrate mit Hexamethylentetramin / The Crystal Structures of Hydrates of Strontium and Barium Hexacyanoferrate(III) with Hexamethylenetetramine. Structural Model for Adducts of the Hexacyanoferrates of Alkaline and Alkaline Earth Metals with Hexamethylenetetramine
Authors: Meyer Hans-Jürgen , Pickardt Joachim
Published: March 2015

By reaction of methanolic solutions of hexamethylenetetramine with aqueous solutions of hexacyanoferrates(III) of strontium and barium resp., crystals of the compounds were obtained. Sr3[Fe(CN)6]2 · 3 C6H12N4 · 18 H2O, tetragonal, space group P42/nmc, Z = 4, a = 1931.8(4), c = 1579.9(4) pm, 1358 reflections. R = 0.066. Ba3[Fe(CN)6]2 · 2 C6H12N4 · 11 Η2Ο. monoclinic. space group P21/n, Ζ = 2, a = 1148.0(4), b = 1369.7(4), c = 1584.5(4) pm, γ = 95.79(3)°, 2583 reflections, R = 0.057. The crystal structures of these adducts are compared with those of other hexamethylenetetramine adducts of alkaline and alkaline earth metal hexacyanoferrates of the general formula M,[Fe(CN)6]y · zC6H12N4 · vH2O recently investigated by us. A structural model for the adducts is presented.
The Molecular Nature of the Hydrophilic Sulfur Prepared from Aqueous Sulfide and Sulfite (Selmi Sulfur Sol)
Authors: Steudel Ralf , Göbel Thomas , Holdt Gabriele
Published: March 2015

Hydrophilic sulfur sols prepared by reaction of aqueous sulfide and sulfite at low pH have been studied by chemical analysis, ion-pair chromatography, and reversed-phase HPLC. The approximate composition of the sol is x(NaHSO4/Na2SO4) ·ySn · zNa2SmO6 with n = 6-10 and m = 4-16. The elemental sulfur Sn accounts for 17% and the polythionate sulfur for 10% of the dry weight (sulfate: 18%). On aging of the sol at 20°C the long-chain polythionates decompose to elemental sulfur and tetrathionate as well as pentathionate. The higher chemical reactivity of this sol compared to S8 is explained by the fact that 45% of the zero oxidation state sulfur (S°) are present as non-S8 molecules.
Stereochemistry of 2,6-Dipyridine Substituted N-Benzyl-4-piperidone Mono- and Dicarboxylates and of the Corresponding Reduction Products
Authors: Holzgrabe U. , Piening B. , Hesse K.-F. , Höltje H.-D. , Worch M.
Published: March 2015

The alkyl N-benzyl-4-piperidone-3-carboxylate (1) is synthesized by a Mannich procedure from pyridine aldehyde, benzylamine and the monoester of acetonedicarboxylate; the corresponding diester 2 is formed by condensation of pyridine aldehyde, benzylamine and dimethyl 3-oxoglutarate. Isomerism is observed with respect to keto-enol tautomerism and cis or trans substitution of the pyridines. The structure of the enol lb (C24H23N3O3) is determined by X-ray analysis: it crystallizes in the triclinic space group P 1̄ with a = 9.965(2), b = 10.476(2), c = 10.838(2) Å, α = 69.48(1), β/3 = 81.56(1), γ = 79.09(1)°, Ζ = 2 and Dx = 1.29 g cm-3. It is refined to R(unweighted) = 0.047 and R(weighted) = 0.045 using 1459 non-equivalent reflections. The structures of la/b and 2a/b were determined by 1H and 13C NMR data. MNDO calculations of 1a/b are discussed. The enols 1/2b are reduced by sodium borohydride. The configuration of the obtained alcohols is determined by NMR data.
Notizen: Kristallstruktur von [Et4N][PBr4]. Strukturkorrelation für Halogenophosphate(III) / Crystal Structure of [Et4N][PBr4]. Structural Correlation for Halogenophosphates(III)
Authors: Sheldrick W. S. , Kiefer J.
Published: March 2015

The tetrabromophosphate(III) anion in [Et4N][PBr4] displays an extremely distorted Ψ-trigonal bipyramidal structure with axial P-Br distances of 2.970(2) and 2.305(2) Å. A structural correlation of bond distances in characterized halogenophosphates(III) indicates that such an asymmetric three-centre Br-P ··· Br interaction represents an energy minimum for isolated anions.
Darstellung und Schwingungsspektren der 35Cl/37Cl-markierten Fluoro-Chloro-Platinate(IV) / Preparation and Vibrational Spectra of 35Cl/37Cl Labelled Fluoro-Chloro-Platinates(IV)
Authors: Erlhöfer P. , Preetz W.
Published: March 2015

All components of the two series Cs2[PtF„35Cl6-n] and Cs2[PtFn
37Cl6-n], including the pairs of geometric isomers for n = 2,3, 4, have been prepared and isolated by ion exchange chromatography on DEAE cellulose. The highly resolved low temperature (80 K) IR and Raman spectra of the pure isotopomers show distinctive isotopic shifts for different vibrational modes up to 10 cm-1. The excellent agreement of the observed values with Teller-Redlich calculations verifies the assignment of all stretching and especially of the narrow deformation bands. For transcomplexes containing 35Cl-Pt-37Cl axes, the lowered symmetry affects the restriction of the rule of mutual exclusion
Mangan(II)-Komplexe mit dem vierzähnigen Stickstoffliganden C12H22N6(L): Synthese von [MnX2L] (X = Cl, Br, I, NCS), Kristallstrukturen von [MnCl2L] und [MnBr2L] / Manganese(II) Complexes with the Tetradentate Nitrogen Ligand C12H22N6(L): Synthesis of [MnX2L] (Χ = Cl, Br, I, NCS), Crystal Structures of [MnCl2L] and [MnBr2L]
Authors: Stolz Peter , Saak Wolfgang , Strasdeit Henry , Pohl Siegfried
Published: March 2015

[MnCl2(C12H22N6)] (1) and [MnBr2(C12H22N6)] (2) are obtained from the reaction of MnX2 (X = Cl, Br) with C12H22N6 in methanolic solution.

In chloroform MnI2, OPPh3, and C12H22N6 react to give [MnI2(C12H22N6)] (3). With small variations of the reaction conditions [MnI2(C12H22N6)] · xCHCl3 (4) may be crystallized. The reaction of [Mn(NCS)2(OPPh3)4] with C12H22N6 in CHCl3 solution gives [Mn(NCS)2(C12H22N6)] · xCHCl3 (5). The structures of 1 and 2 were determined from single crystal X-ray diffraction data. The isotypic compounds crystallize in the orthorhombic space group Pbcn with Z = 4; 1: a = 1592.4(1), b = 785.0(1), c = 1270.7(1) pm; 2: a = 1590.0(1), b = 802.6(1), c = 1316.6(1) pm. C12H22N6 acts as a tetradentate ligand. The isolated complexes exhibit a twofold symmetry.

Manganese(II) is in a six-coordinate environment, which can be described better as a distorted tetrahedron with two additional Mn-N bonds rather than as a distorted octahedron.

The Mn-N bond lengths are 229.9(1) and 248.7(1) pm for 1 and 228.2(3) and 248.4(3) pm for 2. The Mn-Hal bond lengths are 239.2(1) (1) and 254.2(1) pm (2)
Über die Darstellung von P-Chlor-substituierten Ν,N′-Dimethylharnstoff-verbrückten Diphosphorverbindungen, deren Enthalogenierung mit Oxalsäurebis(trimethylsilylester) und anschließende Oxidation mit Tetrachlororthobenzochinon / Preparation of P-Chloro-Substituted N′,N′-Dimethylurea-Bridged Diphosphorus Compounds, their Dehalogenation with Oxalic Acid Bis(trimethylsilyl) Ester and Subsequent Oxidation with Tetrachloroobenzoquinone
Authors: Vogt Roland , Schmutzler Reinhard
Published: March 2015

Reaction of N,N′-dimethyl-N,N′-bis(trimethylsilyl)urea (1) with dichlorophosphines. RPCl2 (R = Et: 14; R = Pr: 15) has furnished the P-chloro-substituted acyclic diphosphorus compounds, 16 and 17. In the analogous reaction of 1 with Ph2PCl the corresponding bis(diphenylphosphino)-substituted derivative, 21 was formed. Dehalogenation of 11, 16 and 17 with oxalic acid bis(trimethylsilyl) ester, 22 has produced the mixed-valent cyclic λ3P,λ4P-diphosphorus compounds, 23-25 in almost quantitative yield. Oxidation of the λ3P atom in 23-25 with tetrachloroorthobenzoquinone, 26 has given rise to partial cleavage of the P-P bond, and only moderate yields of the products, 29, 31 and 32, have been obtained. The characterization of the various compounds obtained rests, especially, on their 1H and 31P NMR spectra, and on a study of their mass spectral fragmentation pattern
Fluorescence Measurements on the Photooxidation of Poly(ethyleneterephthalate) Films and a Photoselective Effect
Authors: Hennecke M. , Keck I. , Lemmert E. , Fuhrmann J.
Published: March 2015

Photooxidation of PET fibres or films creates fluorescent by-products which are separated in wavelength from the intrinsic fluorescence of PET. An experimental technique is described which allows the study of the dependence of photooxidation on wavelength by the fluorescence of only a single specimen. Furthermore, using polarized fluorescence, the conservation of photoselected orientation can be investigated if the photooxidation is carried out with linearly polarized light. Evidence is presented that photooxidation of PET films takes place under partial conservation of the photoselected molecular orientation.
Der Halbleiter-Metall-Übergang in Pyrochloren des Systems Ln2-xCuxRu2O7-z (Ln = Pr, Sm, Eu, Gd, Dy) / The Semiconductor-Metal Transition in Pyrochlors of the System Ln2-xCuxRu2O7-z (Ln = Pr, Sm, Eu, Gd, Dy)
Authors: Kürthy G. Mayer-von , Wischert W. , Kemmler-Sack S.
Published: March 2015

In the pyrochlor system Ln2-xCuxRu2O7-z a partial substitution of Pr bv Cu is observed for x ≾ 0.375. With increasing x a gradual semiconductor-metal transition occurs. The change of sign of TCR from negative to positive is observed for ρ ∾ 6 × 10-3 Ω cm (x = 0.2). The presence of variable range hopping in the insulating regime strongly suggests that the metal-semiconductor transition is of Anderson type. For the pyrochlores of type Ln1.625Cu0.375Ru7-z with the smaller rare earth ions Sm, Eu, Gd, Dy the metallic conductivity is absent and localization of Anderson type occurs.
(Dimethylphosphito-P){tris[2-(diphenylphosphino)ethyl]-phosphine-P,P′,P″,P″′}platinum(II)-chloride: Synthesis and Structural Characterization
Authors: Brüggeller Peter , Hübner Thomas , Gieren Alfred
Published: March 2015

Controlled hydrolysis at low temperatures of (trimethylphosphito-P){tris[2-(diphenylphosphino)ethyl]phosphine-P,P′,P″,P″′}platinum(II)-dichloride, [Pt(PP3)(P(OMe)3)]Cl2 (2), leads to the title compound (1) in nearly quantitative yield. The 31P NMR spectrum of 1 shows an AMX3 pattern consistent with the formulation as [Pt(P(O)(OMe)2)(PP3)]Cl. 1 has been further characterized by an X-ray structure analysis, which shows a trigonal-bipyramidal stereochemistry with the (dimethylphosphito)-ligand occupying an axial position. NMR and X-ray results of 1 and [PtH(PP3)](BPh4) (3) are compared.
Notizen: Kristallstruktur von 1,1-Dichlor-3,5-diphenyl-4-H-1,2,4,6-λ4-selenatriazin, SeCl2C2N3H(C6H5)2 / Crystal Structure of 1,1-Dichloro-3,5-diphenyl-4-H-1,2,4,6-λ4-selenatriazine, SeCl2C2N3H(C6H5)2
Authors: Fenske Dieter , Ergezinger Christina , Dehnicke Kurt
Published: March 2015

The title compound has been prepared as a byproduct of the reaction of Se2Cl2 with Ν,Ν,N′-Tris(trimethylsilyl)benzamidine in CH2Cl2 solution. [SeCl2(HNC2N2Ph2)]2 was characterized by an X-ray structure determination. Space group P21/n, Z = 2, 2979 observed independent reflexions, R = 0.032. Lattice dimensions (-65 °C): a = 1050.1(4), b = 1018.9(4), c = 1402.1(6) pm; β = 99.78(3)°. The compound forms centrosymmetric dimeric molecules with SeCl2Se bridges (bond lengths 241.6(1) and 339.3(1) pm), the selenium atoms being members of nearly planar [xxx] selenatriazine rings with Se—N bond lengths of 182.2(2) and 181.5(2) pm.
Notizen: Reaktionen mit Dimethylcarbonat, 5 Methylierung der Pyrimidin-Basen der Nucleinsäuren / Reactions with Dimethyl Carbonate, 5 Methylation of the Pyrimidine Bases of Nucleic Acids
Authors: Wal Helmut Jansen in de , Lissel Manfred
Published: March 2015

The methylation of the pyrimidine bases of nucleic acids by dimethyl carbonate is described compared to dimethyl sulphate. The reaction needs higher temperature, a base and the help of 18-crown-6 and DMF as cosolvent.
Ein Beitrag zur Synthese neuer chiraler Phosphanliganden / Synthesis of a New Chiral Phosphine Ligand
Authors: Fenske Dieter , Merzweiler Kurt
Published: March 2015

The new chiral diphosphine 2 was synthesized from mucochloric acid. The structure of the NiI2-complex 7 was determined by single crystal X-ray analysis. 7 crystallizes in the orthorhombic space group P212121. The lattice constants (at 180 K) are: a = 914.1(2); b = 1422.0(3); c = 4112.5(10) pm.
Synthese, IR-Spektrum und Kristallstruktur des Amidinatokomplexes [Na(15-Krone-5)][Ph—C(NSiMe3)2SnCl3F] / Synthesis, IR Spectrum, and Crystal Structure of the Amidinato Complex [Na(15-Crown-5)][Ph — C(NSiMe3)2SnCl3F]
Authors: Kildea John David , Hiller Wolfgang , Borgsen Beatrice , Dehnicke Kurt
Published: March 2015

The title compound [Na(15-crown-5)][C6H5–C(NSiMe3)2SnCl3F] is synthesized by the reaction of sodium fluoride with Ph—C(NSiMe3)2SnCl3 in acetonitrile solution in the presence of 15-crown-5 as white, moisture-sensitive crystals. The complex is characterized by its IR spectrum as well as by an X-ray structure determination. Space group P212121 Z = 4, 4897 observed independent reflexions, R = 0.094. Lattice dimensions at 20°C: a = 1065.7(2), b = 1431.0(2), c = 2325.6(3) pm. The compound forms ion pairs with a bent Sn–F–Na bridge (bonding angle 119.0(5)°) and distances Sn–F of 196(1) and Na–F of 232(1) pm. The tin atom is in a distorted octahedral environment defined by the two N atoms of the symmetrically coordinated amidinato ligand, by three chlorine atoms, and by the fluorine ligand; the latter is in a trans-position relative to one of the nitrogen atoms.
Zur Komplexchemie der Alkalimetalle: Kristallstruktur von RbLiS / On the Complex Chemistry of the Alkali Metals: The Crystal Structure of RbLiS
Authors: Sabrowsky Horst , Hippler Karin , Hitzbleck Rolf-Dieter , Sitta Stephan , Thimm Alfred , Vogt Petra , Wortmann Regina
Published: March 2015

The colourless compound RbLiS has been prepared as described earlier (H. Sabrowsky, A. Thimm, and P. Vogt-Mertens, Z. Naturforsch. 40b, 1759 (1985)) and its crystal structure determined by X-ray diffraction. Very hygroscopic RbLiS crystallizes in the tetragonal space group P4/nmm (Z = 2) with the cell parameters a = 4.424(3) Å, c = 7.255(2) Å. The structure was solved from 1635 counter reflections (155 symmetry independent reflections) by Patterson and Fourier methods (R = 0.031; wR = 0.031).

The structure is characterized by layers of ∞
2[LiS4/4]-tetrahedrons separated by double-layers of Rb+ to form a PbFCl-type geometry.
Substitutionsreaktionen an der N-Chlornitrenogruppe des [WCl4(NCl)]2. Die Kristallstrukturen von [CH3CN—WCl4(NSMe)] und [WNCl3 · NC—CH3]4 / Substitution Reactions at the N-Chloronitreno Group of [WCl4(NCl)]2. The Crystal Structures of [CH3CN—WCl4(NSMe)] and [WNCl3 · NC—CH3]4
Authors: Görge Astrid , Patt-Siebel Ute , Müller Ulrich , Dehnicke Kurt
Published: March 2015

[WCl4(NCl)]2 reacts in acetonitrile with the trimethylsilyl compounds Me3SiSR (R = Me, Ph), and Me3SiESiMe3 (E = S, Se), with substitution of the chlorine atom of the N-chloronitreno group W=N–Cl and formation of CH3CN–WCl4(NSR) and CH3CN–WCl4(NEN)WCl4–NCCH3, respectively. Excess Me3SiBr reacts with CH3CN–WCl4(NSMe) to afford CH3CN–WBr4(NSMe). [CH3CN–WNCl3]4 was obtained from CH3CN–WCl4(NCl) and N(SiMe3)3. The products were characterized by their IR spectra. Two X-ray crystal structure determinations were also carried out. CH3CN—WCl4(NSMe) forms twinned crystals, and only non-overlapping reflexions of one of the twin individuals were used for the structure determination (846 unique values, R = 0.055). Crystal data: a = 592.4(2), b = 758.8(2), c = 1203.7(8) pm, β = 95.06(4)°, monoclinic, space group P21/m, Z = 2. The compound is a monomer in which the acetonitrile ligand is situated in the trans position to the W≡N–S̱̅–Me group. The bond lengths (W≡N 174(2), N–S 161(2) pm) and bond angles (WNS 176(1), NSC 102.1(9)°) are in agreement with the proposed formula. Crystal data for [CH3CN–WNCl3]4: a = 1009.5(2), b = 1274.5(2), c = 1287.9(2) pm, β = 108.17(1)°, monoclinic, space group P21/c, Z = 2 (2113 unique reflexions, R = 0.057). The compound forms tetrameric units, in which the W atoms form a square and are linked with one another via N atoms at alternating distances (W=N 171(2), W–N 207(2), W–NCMe 238(2) pm).
Zur Kenntnis der Hydroxidhalogenide des Bariums. Kristallstruktur und Schwingungsspektren von Ba[O(H,D)]X · 2 (H,D)2O (X = Cl, Br) / Barium Hydroxide Halides. Crystal Structure and Vibrational Spectra of Ba[O(H,D)]X · 2 (H,D)2O (X = Cl, Br)
Authors: Lutz Heinz Dieter , Kellersohn Thomas , Beckenkamp Konrad
Published: March 2015

The quaternary systems Ba(OH)2—BaCl2—H2O and Ba(OH)2—BaBr2—H2O were studied with the help of X-ray and neutron diffraction as well as IR, Raman, DTA, and TG methods. The following compounds have been established or confirmed: Ba(OH)Cl · nH2O (n = 0, 1/2, 2) and Ba(OH)Br · H2O (n = 0, 1/2, 2). The crystal structures (of hitherto unknown structure type) of Ba(OH)Cl- 2 H2O and Ba(OD)Cl · 2 D2O were determined by single crystal X-ray methods and neutron powder diffraction (space group P4/nmm, Z = 2, 621 unique reflections, R = 8.8 and 1.9%, respectively). Whereas the hydroxide ion in this layer structured compound is non-hydrogen bonded, i. e. no Η-bond donor group, nor it is bound to the Ba2+ ions, the water molecules are involved in strong Η-bonds to adjacent OH- ions. The coordination of the barium ions is monocapped tetragonal antiprismatic (4 H2O and 5 halide ions). The IR and Raman spectra of Ba(OH)X · 2 H2O (X = Cl, Br) are assigned and discussed in terms of hydrogen bonding, isotopic shifts, and intermolecular coupling of the bands observed. The stretching modes of the OH- ions (3672 and 3667 cm-1, 95 K) are shifted to higher wavenumbers by about 100 cm-1 as compared with those of free OH- ions.
Thiobenzamid-thiobenzimid-bromo-kupfer(II), [Cu(PhCSNH2)(PhCSNH)Br]2 / Thiobenzamide-thiobenzimide-bromo-copper(II), [Cu(PhCSNH2)(PhCSNH)Br]2
Authors: Souza Pilar , Arquero Agueda , García-Onrubia Azucena , Fernández Vicente , Leiva Ana María , Müller Ulrich
Published: March 2015

The title compound 1 was obtained by the reaction of CuBr2 and thiobenzamide in methanol. Its magnetic susceptibility and its EPR spectrum show it to be a Cu(II) compound. The two different ligands PhCSNH2 (2) and [PhCSNH]- (3) show up by distinct absorption bands in the IR spectrum. The crystal structure of 1 was determined by X-ray diffraction (1289 observed, unique reflexions, R = 0.048). Crystal data: monoclinic, space group P21/n, Z = 2, a = 912.0(2), b = 1859.7(8), c = 1006.2(6) pm, β = 110.73(4)°. There are dimeric, centrosymmetric molecules in which the copper atoms are linked via the sulfur atoms of either 2 or 3, probably 3. The copper atoms show the coordination of a flattened tetrahedron.
Synthese und Kristallstruktur von N,N′-Bis(trimethylsilyl)benzamidinato-dichlorogold, Ph— C(NSiMe3)2AuCl2 / Synthesis and Crystal Structure of N,N′-Bis(trimethylsilyl)benzamidinato-dichlorogold, Ph — C(NSiMe3)2AuCl2
Authors: Hiller Wolfgang , Strähle Joachim , Zinn Alfred , Dehnicke Kurt
Published: March 2015

Ph—C(NSiMe3)2AuCl2 has been prepared by the reaction of N,N,N′-tris(trimethylsilyl)-benzamidine with AuCl3 in CH2Cl2 suspension, forming orange-red crystals, which were characterized by an X-ray structure determination.

Space group P21/n, Z = 4, 2358 observed independent reflexions, R = 0.028. Lattice dimensions (20°C): a = 695.9(3); b = 1576.1(3); c = 1830.9(3) pm; β = 94.27(3)°. The compound forms monomeric molecules, in which the gold atom is in a square planar arrangement of the two nitrogen atoms of the benzamidinato chelate (Au—N 201.6(7); 203.3(6) pm) and by two chlorine atoms (Au—Cl 227.9(3); 228.5(2) pm).
Synthese und Kristallstruktur des Imidokomplexes {TaCl4NC(Ph)[N(SiMe3)2]}2 · 2 CH2Cl2 / Synthesis and Crystal Structure of the Imido Complex {TaCl4NC(Ph)[N(SiMe3)2]}2 · 2 CH2Cl2
Authors: Merzweiler Kurt , Fenske Dieter , Hartmann Eva , Dehnicke Kurt
Published: March 2015

The title compound has been prepared by the reaction of N,N,N′-tris(trimethylsilyl)benzamidine with tantalum pentachloride in CH2Cl2 suspension, forming amber-coloured, moisturesensitive crystals, which were characterized by an X-ray structure determination. Space group P 21/n, Z = 2, 4895 observed independent reflexions, R = 0.059. Lattice dimensions (-65°C): a = 1165.2(6), b = 1335.4(6), c = 1629.0(7) pm, β = 93.23(4)°. The complex forms centrosymmetric molecules dimerized via chloro bridges TaCl2Ta with TaCl bond lengths of 247.2(2) and 277.1(2) pm, the longer one being in trans-position to the imido group, which can be formulated

as [xxx] (bond lengths Ta=Ν = 183.5(8), C=N = 134(1) pm, bond angle TaNC = 162.7(7)°).
Proton-induzierte Kopplung eines tert-Butylisonitril-mit einem Phenylcarbin-Liganden am Wolfram / Proton-Induced Coupling of one tert-Butylisonitrile with one Phenylcarbyne Ligand at Tungsten
Authors: Filippou Alexander Constantin , Grünleitner Walter
Published: March 2015

A good entry to highly substituted phenylcarbyne complexes of tungsten containing tert-butyl-isonitrile ligands is provided via Br(CO)2(pic)2W≡CC6H5 (1) (pic: γ-picoline). The first step includes the replacement of the picoline ligands in 1 by t-BuNC in refluxing CH2Cl2 to give Br(CO)2(t-BuNC)2 W≡CC6H5 (2) in high yield. Complex 2 is then transformed with excess t-BuNC in toluene at 90°C to the carbonyl free carbyne complex trans-Br(t-BuNC)4W≡CC6H5 (3). The monocarbonyl substituted analogue of 3, Br(CO)(t-BuNC)3W≡CC6H5 (4), is observed by IR spectroscopy as an intermediate of this reaction. Its preparation is achieved by the CoCl2 catalyzed decarbonylation of 2 in the presence of one equivalent of t-BuNC. trans-Br(t-BuNC)4W≡CC6H5 (3) and the analogous iodocompound trans-I(t-BuNC)4W≡CC6H5 (5) react with HX (X = Br, I) to give respectively, Br2(t-BuNC)3W[(t-Bu)HN—C≡C—C6H5] (6) and I2(t-BuNC)3W[(t-Bu)HN—C≡C—C6H5] (7) in high yield. Complexes 6 and 7 contain a 4e-donor acetylene ligand resulting from the proton induced coupling of one tert-butylisonitrile with the phenylcarbyne ligand at the tungsten center. The reaction of complex 4 with HBr leads also to the coupling product Br2(CO)(t-BuNC)2W[(t-Bu)HN—C≡C—C6H5] (8), the carbonyl containing analogue of 6, in low yield. With one equivalent of t-BuNC and TlPF6 compounds 6 and 7 are converted to the cationic complexes [Br(t-BuNC)4W[(t-Bu)HN—C≡C—C6H5]]+PF6
- (9) and [I(t-BuNC)4W[(t-Bu)HN—C≡C—C6H5]]+PF6
- (10) respectively. The analogous chloro compound [Cl(t-BuNC)4W[(t-Bu)HN—C≡C—C6H5]]+PF6- (11) is obtained by halogen exchange from 10 and PPN+Cl-. The composition and structure of the new complexes 3, 4, and 6—11 have been determined by elemental analyses, IR, 1H NMR, 13C NMR and mass spectra.
Umwandlungen zwischen Vinyliden- und Alkylidin-verbrückten Dreikernclustern / Interconversions between Vinylidene and Alkylidyne Bridged Trinuclear Clusters
Authors: Bernhardt Wolfgang , Schacht Hans-Thomas , Vahrenkamp Heinrich
Published: March 2015

Based on the observation that the alkylidyne bridged cluster HFeCo2(CO)9(μ3-C—CH3) spontaneously loses H2 to form the vinylidene bridged cluster FeCo2(CO)9(μ3-C=CH2), the interconversions between these types of ligands on mixed trinuclear clusters were investigated. It was found that in all cases clusters of the type HM3μ3-C—CH2R) could be transformed into clusters of the type M3(μ3-C=CHR); for M3 = FeCo2, FeCoMo, RuCoMo, RuCoW, OsCoMo, OsCoW; for R = H and in one case CH3; for dehydrogenation by thermolysis and in one case H+/H- elimination. Conversely, hydrogenation of the vinylidene bridged clusters to the alkylidyne bridged clusters was only possible for the FeCoMo, RuCoMo, and RuCoW systems, for the unsubstituted C=CH2 ligand, and for elemental hydrogen as the reagent. Together with previous observations this leads to the conclusion that among the interconvertible alkyne, vinylidene, and alkylidyne ligands the vinylidene unit represents the most stable entity on trinuclear clusters.
π-Complexes of p-Block Elements: [(η6-C6Me6)Sn(AlCl4)2]2•3 C6H6 — a Dimeric Coordination Compound of Hexamethylbenzene with Sn(AlCl4)2
Authors: Schmidbaur Hubert , Probst Thomas , Steigelmann Oliver , Müller Gerhard
Published: March 2015

Dimeric (η6-hexamethylbenzene)tin(II)bis(tetrachloroaluminate), [(η6-C6Me6)Sn(AlCl4)2]2, has been obtained from the reaction of anhydrous SnCl2, AlCl3, and hexamethylbenzene in the molar ratio of 1:2:1 in benzene as a solvent. The complex, which crystallizes in the triclinic space group PĪ, contains a folded eight-membered ring Al2Sn2Cl4
2+, with the two tin(II) centers linked by two bidentate bridging AICl4- counterions. Each tin(II) atom is η6-bonded to a hexamethylbenzene ring at a distance of 2.45 Å — the shortest Sn-to-arene distance ever found in the tin(II)/arene system. Each tin(II) atom is further connected to another AICl4- anion, also acting as a bidentate ligand, but without contacts to other tin(II) centers. The three crystal benzene molecules show no specific metal contacts.