bluuebunny/crossref_metadata_2025_split huggingface dataset:
Synthesis and Crystal and Molecular Structure of trans-Dichloro(ethanedial dioximato(1—)-N,N')(ethanedial dioxime-N,N')rhodium(III)
Authors: Mégnamisi-Bélombé Michel 
Published: March 2015

Abstract
trans-Dichloro(ethanedial-dioximato)(ethanediaI-dioxime)rhodium (III), RhCl2(GH)(GH2), has been synthesized and its structure determined by single crystal X-ray diffraction at room temperature. C4H7Cl2N4O4Rh, Mr = 348.94. monoclinic space group P21/ɑ; a = 10.543(3), b = 8.363(2), c = 11.512(3)Å ; β = 92.79(2)°; V = 1024Å3; Z = 4; Dc = 2.26 Mg m-3. Final Rw = 0.075 for 2035 reflections and 139 parameters. The coordination geometry around Rh is a dis­torted (4+2) octahedron, with four chelating N atoms lying in the equatorial plane and the two Cl atoms in the apical positions. The H atoms of the oxime groups are involved in relatively weak intramolecular O-H-O bridgings, as well as in very strong intermolecular bridgings which extend throughout the crystal structure and propagate nearly parallel to the [101] crystallographic direction.
Synthese und Struktur von μ-Bromo-μ-dioxo-bis( phthalocyaninato-niob(V))tribromid, [(PcNb)2O2Br]+Br3
-, einem zweikernigen Phthalocyaninatokomplex / Synthesis and Structure of μ-Bromo-μ-dioxo-bis(phthalocyaninato-niobium(V))tribromide, [(PcNb)2O2Br]+Br3
-, a Dinuclear Phthalocyaninato Complex
Authors: Gingl Franz , Strähle Joachim 
Published: March 2015

Abstract
dioxo-bis(phthaIocyaninato-niob(V))tribromid, [(PcNb)20 2Br]+BrJ, einem zweikernigen Phthalocyaninatokomplex Synthesis and Structure of i w-Bromo-/ i/-dioxo-bis(phthalocyaninato-niobium(V))tribromide, [(PcNb)20 2Br]~Br3 , i w -Brom o-^-dioxo-bis(phthalocyaninato-niobium (V))tribrom ide. Synthesis. Crystal Structure
Lithio-di-tert-butylfluorsilyl-tert-butylphosphan — Kristallstruktur und Reaktionen/Lithio-di-tert-butylfluorosilyl-tert-butylphosphane — Crystal Structure and Reactions
Authors: Andrianarison Mbolatiana , Klingebiel Uwe 
Published: March 2015

Abstract
Di-tert-butylfluorosilyl-tert-butylphosphane (1) reacts with n-C4H9Li to give the lithium salt (CMe3)2SiF-PLi(THF)3CMe3 (2) and butane. The crystal structure of 2 has been determined. Fluorosilylphosphanes of the type (CMe3)2SiFP(R)CMe3 [R = SiMe3 (5), SiCl2Me (6). SiCl3 (7), SiF2C6H5 (8), BFN (SiMe3)2 (9), SiClMeP(CMe3)SiF(CMe3)2 (10)] are obtained in the reaction of 2 with halogenosilanes and -borane. 6 and 7 undergo rearrangement via chloro-fluoro exchange reaction to give (CMe3)2SiCl-P(SiClRF)CMe3 [R = Cl (11), Me (12)].
Bor-stabilisierte N,O-Carbene, I Triphenylbor-Addukte von Siloxy-und Hydroxyalkylisocyaniden und spontane At-Ylid-Bildung / Boron-Stabilized N.O-Carbenes, I Triphenylboron Adducts of Siloxy- and Hydroxyalkyl Isocyanides and Spontaneous Formation of Ate-Ylids
Authors: Fehlhammer Wolf Peter , Hoffmeister Hans , Stolzenberg Heribert , Boyadjiev Borislav 
Published: March 2015

.
Triphenylboron adducts of 2- and 3-hydroxyalkyl isocyanides spontaneously undergo intramolecular cyclization to give oxazolidin-2-ylidene and perhydrooxazin-2-ylidene boron complexes, respectively. The same compounds are obtained by methanolysis of the stable species Ph3B-CNCR1R2CR3R4-OSiMe3 (R1, R2, R3, R4 = H, alkyl) (2a-i) and Ph3B-CN(CH2)3-OSiMe3 (2j)IR, 1H NMR, 13C{H} NMR. and mass spectra of the new compounds are reported.
Na5InTe4 und Na5In2Te6 — Erste Beispiele für Neso-sowie Ditelluro-verbrückte Inotelluroindate/Na5InTe4 and Na5In2Te6 — First Examples of Neso-and Ditelluro-Bridged Inotelluroindates
Authors: Eisenmann Brigitte , Hofmann Achim , Zagler Roland 
Published: March 2015

Abstract
Single crystals of the ternary com pounds Na5InTe4 and Na5In2Te6 have been grown from the melt und have been investigated by X-ray single crystal techniques.
Na5InTe4: orthorhombic, space group Pbcn; Z = 8; a = 742.7(4) pm, b = 2015.4(8) pm, c = 1773.3(6) pm; Na5In:Te6: orthorhombic, space group Cmc21; Z = 8; a = 902.1(4) pm, b = 1536.1(5) pm , c = 2356.5(6) pm.
The crystal structure of Na5InTe4 contains isolated InTe4 tetrahedra (mean bond length: 278.8 pm). In the crystal structure of Na5In2Te6 InTe4 tetrahedra are connected through common vertices to "Zweiereinfach"-chains. Two neighbouring chains each are joined further to ribbons through Te -Te bridges between every second InTe4 tetrahedron.
Synthese und Kristallstruktur von l,13-Bis(8-chinolyl)- 1,4,7,10,13-pentaoxatridecan-diquecksilber(I)-diperchlorat
Authors: Brodersen Klaus , Zimmerhackl Jörg 
Published: March 2015

1,13-Bis(8-quinolyl)-1,4,7,10,13-pentaoxatridecane-dimercury(I)-diperchlorate is formed by the reaction of 1,13-bis(8-quinolyl)-1,4,7,10,13-pentaoxatridecane in ethanol with an aqueous solution of dimercury(I)-diperchlorate.
It crystallizes in the triclinic space group P Ī with a = 1020.6(2), b = 1200.6(8), c = 1441.1(6) pm , α = 69.60(5)°, β = 83.04(13)°, y = 66.53(4)° and Z = 2. The crystal structure was determined by X -ray diffraction and refined to an R-value o f 0.079.
The Hg2
2+ -ion is coordinated to both nitrogen atoms and four oxygen atoms of one molecule of the ligand. By changing four C - O torsional angles from trans to gauche, the ligand adopts a helical, chiral configuration around the Hg2
2+-ion. The CIO4
--ions are not coordinated to the Hg2
2+-ion.
The Reactions of Dioxobis(acetylacetonato)moIybdenum, MoO2(acac)2, with Tetrathiomolybdate and Tetrathiotungstate. High Formation Tendency of the {Mvi(μ-S)2Miv} (μ-S )2MVI} Group and the [MVI,S3(S2)]2- Type Ligand (M = Mo, W)
Authors: Herberhold Max , Jin Guo-Xin , Müller Achim , Penk Michael 
Published: March 2015

1
Tetraphenylphosphonium tetrathiometalates, (PPh4)2MS4 (M = Mo, W), react with MoO2 (acac)2 (2:1) in boiling acetonitrile in redox processes to give mixed-crystal compounds (as expected) of the approximate composition (PPh4)2[Mo3O1.9S8.1] (1) and (PPh4)2[Mo1.4W1.6O1.3S8.3] (2), respectively. and 2 were characterized by single crystal X-ray structure analyses. The various anions o f 1 and 2 contain {MVI(μ-S)2MoIVO (μ-S )2MVI} cores (M = Mo (1); Mo, W (2); bond angle M ··· Mo ··· M = 151.3° (1) 152.2 - 154.3° (2)), which have high formation tendencies. The terminal positions are occupied by S and O atoms. The trinuclear anions of 1 correspond to the type [XYMo(μ-S)2MoO(μ-S)2MoSX ]2- (X = O, S; Y = S, S2). In 2 there are two sets of anions of the type [XYM(μ-S)2MoO(μ-S)2WS2]2- and [ZSM (μ-S)2MoO(μ-S)2MZS]2- (Z = Sn/Om) in the ratio o f 2:1, occupying two symmetry-independent sites in the unit cell. Complex 2 is the first structurally characterized mixed-metal Mo - W thiometalate.
Convenient Sign Determination of Various Coupling Constants in Alkynylplatinum(II) Phosphine Complexes
Authors: Wrackmeyer Bernd 
Published: March 2015

(1)
The utilization of two-dimensional (2 D) 13C /1H , 31P/1H and 195Pt/1H heteronuclear shift correlations for the sign determination of various coupling constants [e.g., 2J(31PPt13C) > 0 (trans), 2J(31PPt13C) < 0 (cis), 3J( 31PPtC13C) > 0 (cis, trans), 4J(31PPtCC1H ) > 0 (trans), 4J(31PCC1H ) < 0 (cis), 3J(195PtCC1H ) > 0, 2J(31PC1H ) < 0, etc.] is demonstrated, using standard equipment. The complexes [trans-(Bu3P)2Pt(C ≡ C -H)2] and [cis-(Et2PCH2CH2PEt2)Pt(C ≡ C - H)2] (2) serve as model compounds.
UV Photoelectron Spectra and Pseudopotential “ab initio” Calculations of Some 4-Membered Cyclic Amides of Group XIV Elements
Authors: Andreocci Marco V. , Cauletti Carla , Stranges Stefano , Wrackmeyer Bernd , Stader Carin 
Published: March 2015

Gas-phase He I and He II photoelectron spectroscopy and Pseudopotential “ab initio” calculations were used to determine the electronic structure of some 4-membered cyclic amides containing Si, Sn and Pb.
The IE splitting on the non-bonding nitrogen-localized m .o .s ., nN
asym(a2) and nN
sym(b2), due to the “through space” interaction is critically affected by the planar ring molecular structure and the coordination of the silicon and tin atoms of the ring.
The pseudopotential “ab initio” model resulted successful in describing the electronic structure of the molecules containing heavy atoms, at a Koopmans’ approximation level.
[Fe4S4l2+-Cluster mit Thioharnstoffliganden: [FeIL3][Fe4S4I3L]' (L = (Me2N)2CS) und [Fe4S4I2L'2](L' = (C4H9NH)2CS)
Authors: Pohl Siegfried , Bierbach Ulrich 
Published: March 2015

(1)
The mixed terminal ligand iron-sulfur clusters [F eIL 3][Fe4S4I3L] and [Fe4S4I2L '2] (2) with the neutral ligands L = (M e2N )2CS and L' = (C4H 9N H )2CS have been synthesized by the reaction o f F eI2L2 with 1.5 equivalents o f Fe(C O )5 and 2 equivalents o f sulfur and by the reaction o f F eI2L '2 with 3 equivalents o f Fe(CO)^ and 4 equivalents o f sulfur, respectively. The crystal structures o f 1 and 2 were determined from single crystal X -ray diffraction data. 1 crystallizes in the triclinic space group P 1 with a = 968.6( 1), b = 1466.2( 1), c = 1679.1(1) pm, a = 91.51(1),/?= 93.43( 1), y = 90.82( 1)°, V = 2379.2 * 106 pm 5, Z = 2, R = 0.054. 2 crystallizes in the m onoclinic space group P2 Jn with a = 930.2(1), b = 1666.1(1), c = 2335.6(1) pm, β = 97.26°, V = 3 5 90.8 x 106 pm 3, Z = 4. R = 0.055. The anion [Fe4S4I3L] o f 1 exhibits a nearly undistorted [Fe4S4]2+ core. The F e - S distance to the thiourea ligand is found at 230.6 pm. The m ost striking feature o f the neutral cluster o f 2 is the very short F e - F e distance (268.7 pm) between the iron atom s with thiourea ligation which is possibly a consequence of back-donation. The F e - S thiourea distances in 2 were found to be 230.8 and 231.5 pm , respectively.
Outer-sphere-CT-Wechselwirkungen in organisch-anorganischen Ionenpaaren, IIa. Isolierung metastabiler Precursorkomplexe und thermischer OSCT-Elektronentransfer zwischen einem organischen π-Radikaldikation und Hexahalogeno-selenat(IV)-Komplexen: Erstmalige Erzeugung von SeCl6 ⨪
Authors: Weiss Robert , Grimmeiss Andreas M. H. 
Published: March 2015

Deeply coloured 1:1 electrolytes of the type Tris(dimethylamino)cyclopropendiylium )2+SeX6
2- (X = Cl, Br) have been obtained as metastable products of a kinetically controlled redox reaction and are compared with their Tellurium counterparts. According to UV and polarographic evidence there is strong OSCT -interaction between the SOMO of the organic moiety as acceptor and the alg*-HOMO of the ns2 anion as donor. The alg* donor capacity of ns2 anions of type EIX6
2- increases with decreasing atomic weight both of the central atom El and the ligand X. This trend and be rationalized on the basis o f a simple qualitative MO argument.
Upon gentle heating the SeX6
2- systems are oxidized by their own counter cation. The novel SeX6⨪-species thus generated either disproportionates (X = Br) or acts as a selective radical halogenating agent (X = Cl) for the organic cation.
Synthesen und Kristallstrukturen von [Ph3PN PPh3]2[Fe2Se2(Se5)2] · 2 DMF und [Ph3PNPPh3]3[Co3 (Se4)6] · 2 DMF / Syntheses and Crystal Structures of [Ph3PN PPh3]2[Fe2Se2(Se5)2] · 2 DMF and [Ph3PNPPh3]3[Co3 (Se4)6] · 2 DMF
Authors: Müller Ulrich , Ha-Eierdanz My-Linh , Kräuter Gertrud , Dehnicke Kurt 
Published: March 2015

The title compounds have been prepared by reactions of sodium polyselenide solutions in DMF with FeCp(CO)2I, and CoCl2 · 6H2O , respectively, in the presence of (Ph3PNPPh3)Cl. They form black crystals, which were characterized by X-ray structure determinations.
[Ph3PNPPh3]2[Fe2Se2(Se5)2] · 2 DMF: Space group P21/c, Z = 2, 2801 observed unique reflexions, R = 0.077. Lattice dimensions at 20 °C: a = 1091.6(7), b = 1247.3(5), c = 3070(2) pm, β = 90.77(4)°. In the dimeric anion the Fe atoms are linked via two bridging Se atoms, and each Fe atom is chelated by an Se5 group. In the crystals, there are alternating layers o f cations and anions.
[Ph3PNPPh3]3[Co3(Se4)6] · 2 DMF : Space group P1̄, Z = 1, 3549 observed unique reflexions, R = 0.108. Lattice dimensions at 20 °C: a = 1496.2(5), b = 1504.8(5), c = 1904.1(6) pm, α = 100.31(2)°,β = 100.60(2)°, γ= 117.18(2)°. In the [Co3(Se4)6]3- ion two [Co(Se4)3]3- units, each with three chelating Se4 groups, are linked to a central Co3+ cation.
Metallkomplexe mit funktionalisierten Schwefelliganden, II . Ruthenium(II)-benzylthiosulfinato Komplexe. Kristallstrukturanalyse von Cp(Ph3P)2Ru[S—S(O)—CH2C6H5]/Metal Complexes of Functionalized Sulfur Containing Ligands, II. Synthesis of Ruthenium (II) B enzyl-thiosulphinato Complexes. X-Ray Structure Determination of Cp(Ph3P)2Ru[S—S(O)—CH2C6H5]
Authors: Weigand Wolfgang , Bosl Gabriele , Robl Christian 
Published: March 2015

(2))
CpRu(PPh3)(L)(SH) (L = PPh3 (1), CO compounds react with N-(benzylsulphinyl) phthalim ides to give the chiral complexes CpRu(PPh3)(L)[S-S(O)-CH2-Ph] (4, 5). For 5, a diastereoselectivity of 10:3 is observed. The compounds 4, 5 have been characterized by their spectroscopic data. The X-ray structure d etermination of 4 shows sulphur-sulphur bond lengths of 204,4(4), 205,5(4) and 205,3(4) pm for three independent molecules.
Synthese, FIR-Spektren und Kristallstrukturen der Pentaselenide K2Se5 und [Na(15-Krone-5)]2Se5 / Syntheses, FIR Spectra, and Crystal Structures of the Pentaselenides K2Se5 and [Na(15-crown-5)]2Se5
Authors: Müller Volker , Frenzen Gerlinde , Dehnicke Kurt , Fenske Dieter 
Published: March 2015

K2Se5 has been prepared by crystallization from a potassium polyselenide solution in DMF. In a similar way [Na(15-crown-5)]2Se5 can be prepared by crystallization from a sodium polyselenide solution in DMF in the presence of 15-crown-5. Both compounds were characterized by FIR spectroscopy as well as by X-ray structure determinations.
K2Se5: Space group P 212121, Z = 4, 1659 observed independent reflections, R = 0.061. Lattice dimensions at - 90 °C; a = 671.5(5), b = 694.9(5), c = 1776.4(9) pm. The compound crystallizes with the K2S5 type structure.
[Na(15-crown-5)]2Se5: Space group P 1̄, Z = 2, 3026 observed indenpendent reflections, R = 0.140. Lattice dimensions at -100 °C: a = 853.7(5), b = 1042.8(10), c = 2011.0(10) pm; α = 88.95(5)°, β = 79.42(5)°, γ = 66.15(5)°. The compound forms an ion triple, in which the sodium ions are coordinated by the five oxygen atoms of the crown ether molecules as well as by the terminal selenium atoms of the pentaselenide chain. The rather high R value is a result of the disordered crown ether molecules.
Reaktionen von CF3SF: Addition an C=S-Doppelbindungen / Reactions of CF3SF: Addition to C = S Double Bonds
Authors: Gombler Willy , Bollmann Gerd 
Published: March 2015

Abstract
Trifluoromethanesulfenylfluoride, CF3SF, adds to the carbon-sulfur double bond to form fluorinated compounds containing a trifluoromethyldisulfanyl group. Reactions of CF3SF with CS2,CF2S,CCl2S and (CF3S)2CS are described.
Electron-and Ligand-Transfer Reactions Involving N,N-Dialkylcarbamates. Synthesis and Molecular Structure of V2[η5-(C5H5)]2[O2CN(C2H5)2]4
Authors: Calderazzo Fausto , Pampaloni Guido , Sperrlea Martin , Englert Ulli 
Published: March 2015

Abstract
Electron-and ligand-transfer reactions of low-valent organometallic compounds of titanium and vanadium with N,N-dialkylcarbamates of titanium(IV) are reported. The reaction of VCp2 (Cp = η5-cyclopentadienyl) with Ti(O2CNEt2)4 affords, inter alia, the dimeric vanadium(III) N ,N-diethylcarbamato derivative V2Cp2(O2CNEt2)4 which has been studied by X-ray diffraction methods. Crystal data; triclinic, space group P1̄ ; a = 10.802(2), b = 11.004(1), c = 8.960(1) Å; α = 112.879(9), β = 102.66(1), γ = 102.42(1)°; V = 902.3(6) Å3; Z = 1; F(000) = 368, ρcalc = 1.282 g cm-3; μ = 5.47 cm-1. It consists of a centrosymmetric dimer, the two vanadium atoms being surrounded by four oxygen atoms of the bridging N,N-diethylcar-bamato groups and by the cyclopentadienyl ligand. The metal atom exhibits a distorted square-pyramidal coordination geometry with the oxygen atoms occupying the basal plane. The reaction of TiCp2(CO)2 or Vmes2 (mes = η6-1,3 ,5 -Me3C6H3) with Ti(O2CNEt2)4 affords Ti(III) and V(III) N,N-diethylcarbamato derivatives by a simultaneous ligand-and electron-transfer reaction. Magnesium N ,N-diisopropylcarbamate, Mg(O2CNPri
2)2, has been obtained by a ligand-transfer reaction between MgCp2 and Ti(O2CNPri
2)3.
Metallionen als Löscher der Huminstoff-Lumineszenz / Metal Ions as Quencher of the Luminescence of Humic Substances
Authors: Scheck Christoph F. , Frimmel Fritz H. , Braun André M. 
Published: March 2015

Abstract
The luminescence of aquatic humic substances in water is quenched over a broad range of pH by paramagnetic metal ions like iron(II) and manganese(II). The efficiency dependents on the pH of the solution and rises with increasing basicity; this parallels the complexing of metal ions by humic substances. No quenching of the luminescence is observed by the addition of aluminium(III).
Schwingungsspektren und Normalkoordinatenanalyse der Acetatohalogenodimetallate M2(O2CCH3)4X2, M = Re, Tc; X = CI, Br/Vibrational Spectra and Normal Coordinate Analysis of Acetatohalogenodimetalates M2(O2CCH3)4X2, M = Re, Tc; X = Cl, Br
Authors: Skowronek J. , Preetz W. 
Published: March 2015

Abstract
The orange-red Tc2(O2CCH3)4Br2 has been prepared for the first time by reaction of [Tc2Br8]2- with glacial acetic acid and acetic anhydride. The IR and Raman spectra have been recorded at 80 K and are compared with those of the analogous compounds Tc2(O2CCH3)4Cl2, Re2(O2CCH3)4Cl2 and Re2(O2CCH3)4Br2. The assignment according to the point group D4h is supported by normal coordinate analysis based on a general valence force field. The quadruple M - M bond is stabilized by the bridging acetato and destabilized by the axial halogeno ligands. The valence force constants fd(MM) are determined to 3,96-4,08 mdyn/Å. The interaction constants fdd(MM/MX), fdd(MM/MO) and fdα (MM/MMO) are about three times higher for the technetates as compared with the rhenates. The stronger interaction between oppo­site bonds in the equatorial ligand sphere is revealed by the stretching interaction constants fdd', which are about two times higher than fdd for M - O bonds at right angles. The strong coupling of the ring co-ordinates implies extensive mixing of the M - O valence and deformation modes. The electronic spectra of Tc2(O2CCH3)4X2, agree with those of the corresponding Re compounds.
Propargyl-, Allenyl- und Alkinyl-Phosphane; Synthese, Reaktivität, Isomerisierung/ Propargyl-, Allenyl- and Alkynyl-Phosphanes; Synthesis, Reactivity, Isomerization
Authors: Lang Heinrich , Lay Uwe , Leise Michael , Zsolnai Laszlo 
Published: March 2015

The synthesis and reactivity of non-coordinated and coordinated propargyl phosphanes are discussed. The isomerization of the propargyl unit in (R)P(Cl)(CH2C ≡ CH ) (3) (R = 2,4,6-tBu3-C6H2O) in the presence of NEt3 yields the allenyl substituted p roduct (R)P(Cl)(CH = C = CH2) (4). However, in the presence of HNEt2 the dimethylenecyclobutane 7 is formed.
Different synthetic pathways for the preparation of LnMP(Ph)m(CH2C ≡ CH)3-m complexes (m = 2: LnM = (η5-C5H5)(CO)2Mn: 10a; LnM = (CO)5Cr: 10b; m = 1: LnM = (η5-C5H5)(CO)2Mn: 13a; LnM = (η5-C 5H4Me)(CO)2Mn: 13b) are described. The synthesis o f the alkynyl substituted phosphane compounds LnMP(Ph)m(C ≡ CR )3-m (m = 2: R = Ph, LnM = (η5-C5H5)(C O )2Mn: 20a; LnM = (CO )5 Cr: 20b; R nBu, LnM = (CO)5 Cr: 20c; m = 1: R = Ph, LnM = (η5-C5H5)(CO)2Mn: 22) was also possible. The reaction of
(η5-C5H4Me)(CO)2,MnPPh (CH2C ≡CH)2 (13 b) with Co2(CO)8 affords in high yields (η5-C5H4Me)(CO)2MnPPh[(η2 -CH2C ≡ CH )Co2(CO )6]2 (15).
All new com pounds have been characterized by analytical and spectroscopic data (IR , 1H -, 13C {1H }-, 31P { 1H } -NMR , MS) and (η5-C5H5)(CO)2MnP(Ph)(CH2C ≡ CH)2 (13a) by X -ray analysis.
Reaktionen von Oxovanadium-Dipicolinatokomplexen mit Benzoylhydrazin. Die Kristallstrukturen von [VO(dipic)(NH2NHC(O)Ph) · NH2NHC(O)Ph · H2O, [C(NH2)3][VO(dipic)(NHNC(O)Ph)] · 2H2O und der „blauen“ Modifikation von [VO(dipic)(H2O)2] · 2H2O / Reactions of Oxovanadium(IV) and -(V) Dipicolinato Complexes with Benzoylhydrazine. Crystal Structures of [VO(dipic)(NH2NHC(O)Ph)] · NH2NHC(O)Ph · H2O · [C(NH2)3][VO(dipic)(NHNC(0)Ph)] · 2H 2O and the “Blue” Modification of [VO(dipic)(H2O) 2] · 2 H2O
Authors: Sundheim Angelika , Mattes Rainer 
Published: March 2015

Abstract
The hydrazino complex [VO(dipic)(NH2NHC(O)Ph)] · NH2NHC(O)Ph · H2O (3) has been prepared by reaction of [VO(dipic)(H2O)] · 2H2O (1) with NH2NHC(O)Ph. (dipic = dianion of pyridine dicarboxylic acid). The hydrazido(2-) complex (guanid)[VO(dipic)(NHNC(O)Ph)] · 2H2O (4) was obtained by reaction of (guanid)[VO2(dipic)]·2H2O and NH2NHC(O)Ph. During the course of this reaction a terminally bonded oxygen atom is abstracted from the vanadium(V) center. 1, 3 and 4 have been characterized by X-ray single crystal diffraction, infrared, Raman and electron spin resonance spectroscopy.
In 1 vanadium is six-coordinate, with the nitrogen atom of the dipic ligand in trans position to the oxo group. The two water molecules are also ligated in mutual trans positions. Vanadium is also six-coordinate in 3 and 4. In both, the dipic ligand is cis oriented with respect to the terminal oxo group. In 3 benzoylhydrazine, and in 4 the hydrazido(2 -) species NHNC(O)Ph act as N,O-chelate ligands, donating their NH2-, respectively NH-group to the remaining equatorial site and their CO-group to an axial site. The V - NH2(213.1(4) pm) and V - NH (190.5(2) pm) bond lengths differ considerably, indicating multiple bond character for the latter. In 3 the V -O(oxo) and V-O (carbonyl) bond lengths are 160.1(4) and 219.1(3) pm, and in 4 160.8(2) and 211.9(2) pm, respectively. Crystal data for 1: space group P 1̄, a = 656.2(2), b = 913.2(3), c - 1075.2(2) pm, α= 111.44(2), β = 100.16(2), γ = 94.81(3)°, Z = 2; 3: space group P1̄, a = 801.4(2), b = 1188.7(11), c = 1353.5(12) pm, α = 72.02(7), β = 88.31(7), γ = 70.60(7)°, Z = 2; 4: space group P 1̄, a = 1018.2(5), b = 1222.5(6), c = 1683.2(6) pm, α = 80.02, β = 89.95, γ = 78.73°, Z = 4.
Messung und Berechnung der CD-Spektren der Biaryl-Alkaloide Ancistrocladein und Dioncophyllein A [1] / Detection and Calculation of the CD Spectra from the Biaryl Alkaloids Ancistrocladeine and Dioncophylleine A [1]
Authors: Fleischhauer J. , Koslowski A. , Kramer B. , Zobel E. , Bringmann G. , Gulden K. P. , Ortmann T. , Peter B. 
Published: March 2015

Abstract
The circular dichroism (CD) of the biaryls ancistrocladeine and dioncophylleine A has been studied. The CNDO/S method in combination with a Boltzmann weighting o f different structures using AM 1 energies has been applied to reproduce the experimental CD spectra o f the two alkaloids with known absolute configuration at with those o f the exciton chirality method.