bluuebunny/crossref_metadata_2025_split huggingface dataset:
Gamma-Ray Bursters and Lorentzian Relativity
Authors: Winterberg F. 
Published: February 2015

Abstract
In the dynamic interpretation of relatively by Lorentz and Poincare, Lorentz invariance results from real physical contractions of measuring rods and slower going clocks in absolute motion against an ether. As it was shown by Thirring, this different interpretation of special relativity can be extended to general relativity, replacing the non-Euclidean with a Euclidean geometry, but where rods are contracted and clocks slowed down. In this dynamic interpretation of the special, (and by implication of the general) theory of relativity, there is a balance of forces which might be destroyed near the Planck energy, reached in approaching the event horizon. In gravitational collapse, the event horizon appears first at the center of the collapsing body, thereafter moving radially outward. If the balance of forces holding together elementary particles is destroyed near the event horizon, all matter would be converted into zero rest mass particles which could explain the large energy release of gamma ray bursters.
31P-NMR-Untersuchungen an linearen Phosphorylphosphazenen / 31P NMR Investigations oil Linear Phosphorylphosphazenes
Authors: Schilling Gerhard , Rabener Claus W. , Lehr Wendel 
Published: February 2015

Abstract
The 31P NMR Spectra of PCl3NPCl2O (1) and the homologous compounds 2-4 do not indicate any rotational isomers in the temperature range 183-413 K. The observed values for ν/2 depend on the viscosity of the solvent and on the temperature of the sample. They are reduced to T1 relaxation effects, where the spin rotational mechanism may be dominant in the case of the small molecules and the PCl3 group.
Chemie polyfunktioneller Liganden, 67 [1]. Die Darstellung von 1.1.1-Tris(dichlorarsinomethyl)ethan, Ethan-1.1.1-tris(methylarsonsäure), 1.1.1- Tris (arsinomethyl )ethan und einem neuen Organocyclotriarsan / Chemistry of Polyfunctional Ligands, 67 [1] The Preparation of 1.1.1-Tris(dichloroarsinomethyl)ethane, Ethane-1.1.1-tris(methylarsonic acid), 1.1.1-Tris(arsinomethyl)ethane and of a New Organocyclotriarsane
Authors: Eilermann Jochen , Lietz Martin 
Published: February 2015

Abstract
1,1,1-Tris(dichlorarsinomethyl)ethane, CH3C(CH2AsCl2)3 (5) can be obtained in the reaction of CH3C(CH2AsNC6H4CH3)3 (4) with gaseous HCl. The heteroadamantane CH3C(CH2AsO)3 (6) reacts with AsCl3 or PCl3 yielding also 5. CH3C(CH2AsO)3, CH3C(CH2AsS)3 and CH3C(CH2AsI2)3 are oxidized with H2O2 to give CH3C[CH2As(O)(OH)2]3 (7) and CH3C[CH2As(O)(OH)2]3·H2O (7 a). CH3C(CH2AsI2)3 and C(CH2AsI2)4 can be reduced with LiAlH4 to give CH3C(CH2AsH2)3 (9) and C(CH2AsH2)4 (12). Oxidation of 9 and 12 leads to the cyclotriarsane compounds CH3C(CH2As)3 (10) and H2AsCH2C(CH2As)3 (13).
Trimethylsilylverbindungen der Vb-Elemente, HI [1]. Tris(trimethylsilyl)- und Tris(trimethylstannyl)bismutan sowie Tetrakis(trimethylsilyl)dibismutan / Trimethylsilyl Derivatives of Vb-Elements, III [1]. Tris(trimethylsilyl)- and Tris(trimethylstannyl)bismuthine as well as Tetrakis(trimethylsilyl)dibismuthine
Authors: Becker Gerd , Rößler Michael 
Published: February 2015

Abstract
Chlorotrimethylsilane and sodium/potassium bismuthide, easily prepared from finely powdered bismuth and sodium potassium alloy in 1,2-dimethoxyethane (DME), react to give tris(trimethylsilyl)bismuthine (1) in 48% yield. When compound 1 is treated with chlorotrimethylstannane all trimethylsilyl substituents are successively replaced by stannyl groups, and tris(trimethylstannyl)bismuthine (4) is obtained. As in analogous reactions of other tris(trimethylsilyl) derivatives of Vb-elements with methyl lithium in diethylether/tetrahydrofuran (THF), one trimethylsilyl group of tris (trimethylsilyl)-bismuthine (1) can also be removed, and lithium bis(trimethylsilyl)bismuthide · 2 THF (5) is formed. With 1,2-dibromoethane bismuthide 6 reacts with metal halogen exchange to give green lustrous needles of tetrakis(trimethylsilyl)dibismuthine (6). In contrast to other dibismuthines described in the literature, this compound is thermally rather stable and can be isolated in preparative amounts. Similar to several distibines a colour change from green to red, resp. orange-red occurs on melting or dissolving dibismuthine 6 in organic solvents.
Elektrochemisches Verhalten der Nitrophenole und ihrer Reduktionsprodukte an Graphitelektroden, II Mechanismus und Kinetik / Electrochemical Behavior of the Nitrophenols and their Reduction Products at Graphite Electrodes, II Mechanism and Kinetic
Authors: Theodoridou Elli , Karabinas Pantelis , Jannakoudakis Dimitrios 
Published: February 2015

Abstract
The mechanism of the electrochemical reactions of 1-nitro-2-naphthol, o-nitrophenol and p-nitrophenol at carbon fibre electrodes is investigated in aqueous solutions with pH= 1-10. The above nitrophenols are reduced to the corresponding amines, which are reoxidized to quinone imines. As the quinone imines are partially hydrolysed to quinones, the kinetic of this hydrolysis reaction is also examined.
In the case of 1-nitro-2-naphthol the hydrolysis rate constant of 1,2-naphthoquinone imine is estimated as a function of pH by cyclic voltammetry.
Cyanato - Kupfer (II) - Komplexe mit organischen Liganden, XX [1]. ESR- und magnetische Untersuchung des Dicyanato-bis(pyridin)kupfer(II)-Komplexes / Cyanato-Copper(II) Complexes with Organic Ligands, XX [1]. ESR and Magnetic Study of Dicyanato-bis(pyridine)copper(II)
Authors: Kohout Jiří , Mroziński Jerzy , Hvastijová Mária 
Published: February 2015

Abstract
The ESR spectra and the temperature dependence of the magnetic susceptibility of Cu(NCO)2(pyridine)2 were measured. The ESR spectrum at room temperature shows a single reversed line; at -130 °C it is isotropic. The susceptibility down to 4.2 K obeys the Curie-Weiss law with a small θ value. These results are interpreted on the basis of the known crystal and molecular structure.
Eine Methode zur C-Methylierung cyclischer β-Dicarbonyl-Verbindungen / A Method for the C-Methylation of Cyclic β-Dicarbonyl Compounds
Authors: Ziegler Erich , Wolfbeis Otto S. , Trummer Iris 
Published: February 2015

Abstract
Cyclic β-dicarbonyl compounds (1,4,7,10) were reacted with either aniline or urea in the presence of trimethoxymethane to give the enamines 2, 5, 8 and 11, resp. The latter were reduced with hydrogen over palladium-charcoal or with the dimethylamine-boron-hydride complex to give the C-methylated β-dicarbonyl compounds 3,6,9 and 12, resp. in moderatly to good overall yields.
Stereoselektive 1.4-Ringöffnung von 1-Aryl-4-methylthio-2-azetidinonen / Stereoselective 1,4-Ringopening of 1-Aryl-4-methylthio-2-azetidinones
Authors: Ongania Karl-Hans 
Published: February 2015

Abstract
The 4-methylthio-2-azetidinones 1a-d react with lithiumiodide/pyridine by stereoselective 1,4-ringopening to the E/Z 3-methylthioprope-noicacid anilides 2b-e. The attempted selective O-alkyl cleavage 1a→1e failed.
Ein Beitrag zur photoinduzierten Desaminierung substituierter 1.2.4-Triazinone / A Contribution to the Photoinduced Desamination of 1,2,4-Triazinones
Authors: Herrmann M. , Parlar H. , Körte F. 
Published: February 2015

Abstract
Solution-phase photoreactions of 4-amino-substituted 1,2,4-triazin-5(4H)-ones (1a-j) in different solvents using UV light with wavelengths greater than 290 nm have been investigated. The results show, that the desamination reaction is influenced by both oxygen and water. The photoexperiments showed clearly that OOH-radicals take part in the first step of reaction.
Neue Ga-Cluster-Verbände im Na7Ga13-II / New Ga-Cluster Compounds: The Structure of Na7Ga13-II
Authors: Frank-Cordier Ursula , Cordier Gerhard , Schäfer Herbert 
Published: February 2015

Abstract
Na7Ga13-II crystallizes in the orthorhombic system, space group Pnma with the constants
a - 1562.5(3) pm, b = 1497.9(3) pm, c = 2167.8(4) pm. The Ga-atoms form Gaj.2 icosahedra and Gais clusters connected to a threedimensional network. The centres of these clusters correspond to the atomic positions of the MgCu2 structure. The number of bonding electrons is related to the Na content of the compound
Darstellung und Kristallstruktur vom Arsen(III)arsen(V)oxidhydroxid As3O5(0H) / Preparation and Crystal Structure of the Arsenic(III) Arsenic(V) Oxide Hydroxide As3O5(OH)
Authors: Bodenstein Doris , Brehm Axel , Jones Peter G. , Schwarzmann Einhard , Sheldrick George M. 
Published: February 2015

Abstract
The title compound was prepared by heating the hydrolysis products of AS2O4 in a sealed tube. The crystal structure was determined and refined to R = 0.058 [P21/c, a = 1250.4(6), b = 459.3(2), c = 1097.6(6) pm, β = 118.08(5)°, Z = 4]. The structure consists of infinite layers, containing pyramidal As(III)O3 and tetrahedral As(V)O4 groups, and stabilised by hydrogen bonding
NMR-Spektroskopie an paramagnetischen Komplexen, XXVII [1] Paramagnetische 1,1' .2,2' .3,3' .4,4' -Oktamethylmetallocene / NMR Spectroscopy on Paramagnetic Complexes, XXVII [1] Paramagnetic 1,1' .2,2' .3,3' .4,4' Octamethylmetallocenes
Authors: Köhler Frank H. , Doll Karl H. 
Published: February 2015

Abstract
The tetramethylated cyclopentadienyl anion has been prepared from tiglinic acid and reacted with solvated metal(II) chlorides to give new octamethylmetallocenes (Me-jcp^M. For M = V, Cr, Co and Ni the paramagnetic 1H and 13C spectra have been recorded. The NMR data prove the molecular structure and show that all methyl groups rotate almost freely. The methyl proton resonance of the nickelocene may serve as a probe for the adjustment of metallocene properties by ring substitution. Based on qualitative MO arguments the correlation of electron spin densities and paramagnetic shifts lead to an understanding of the signal splitting of cobaltocenes. From the electronic point of view the octamethylmetallocenes may be regarded as being in vers to 1,1'-dimethylmetallocenes
Photochemisches Verhalten von Bis(trifluormethylthiyl)trithiocarbonat in Lösung / Photochemical Behaviour of Bis(trifluoromethylthiyl)trithiocarbonate in Solution
Authors: Schlosser Karl 
Published: February 2015

Abstract
Bis(trifluoromethylthiyl)trithiocarbonate shows electronic transitions at 496 nm (nπ*), 299 nm {ππ*) and 259 (nσ*). Photolysis with 254 and 300 nm light at 200 and 309 K in pentane, and at 371 K in heptane yields a mixture of CS2 and perfluorinated compounds such as F3CSCF3, F3CSSCF3, (F3CS)3C-C(SCF3)3, (F3CS)2C=C(SCF3)2, (F3CS)3CH and F3CS-substituted solvent. The concentration of these newly formed products versus time of irradiation has been monitored. The primary photochemical process is the intramolecular decomposition into CS2 and F3CS- and F3O radicals which dimerize in a solvent cage. The formation of (F3CS)3C-C(SCF3)3 is interpreted in terms of a competition between this combination process and trapping of trifluoromethyl radicals by (FsCS)2CS, forming (F3CS)3C-, which subsequently dimerizes. On irradiation at 496 nm (nπ*) no photochemical process has been observed
The Hei and HeH Photoelectron Spectra of [Fe*?3-C3H5(CO)3X] and [Fe^3-C4H7 (CO)3X] (X = Cl, Br, I) and [CoC3H5(CO)3]
Authors: Louwen Jaap N. , Hart Jaap , Stufkens Derk J. , Oskam Ad 
Published: February 2015

Abstract
By means of UV photoelectron spectroscopy (UPS) the electronic structures of [Feη3.C3H5(CO)3X], [Feη3-(2-CH3C3H4)(CO)3X] (X = Cl, Br, I) and [Co(C3H5)(CO)3] have been studied. Detailed assignments are possible and surprisingly low ionization energies (as low as 8.19 eV) are found for iodine lone pair type Orbitals. From the spectra a large difference in π backbonding is found between the cobalt and iron complexes
Komplexe mit alkylsubstituierten Phosphinomethanen und -methaniden, III [1] Strukturchemie dreigliedriger Brückenliganden, III [2] Bis(dimethylphosphino)metlian als Brückenligand in einem dimeren Ag(I)-Komplex / Complexes with Alkyl Substituted Phosphinomethanes and -methanides, III [1] Structural Chemistry of Three-membered Bridging Ligands, III [2] Bis(dimethylphosphino)methane as a Bridging Ligand in a Dimeric Ag(I) Complex
Authors: Karsch Hans H. , Schubert Ulrich 
Published: February 2015

Abstract
[(Me2PCH2PMe2)]2Ag2](PF6)2 has been prepared and characterized by an X-ray structure analysis. It crystallizes in the space group Pbca with a - 1117(1), b = 1768(5) and c = 1315(2). The dication forms an eight membered centrosymmetric ring, the Ag and P atoms being nearly coplanar. Ag-Ag* 304.1(2) pm. The structure is compared with that of the free ligand [15] and of an analogous Ph2PCH2PPh2 complex of Au(I) [9]
Eine neue Synthese, das Schwingungsspektrum und die Kristallstruktur von Tetraphenylarsonium-hydrogendichlorid As(C6H5)4[Cl2H] / A New Synthesis, the Vibrational Spectrum and the Crystal Structure of Tetraphenylarsonium Hydrogendichloride As(C6H5)4Cl2H]
Authors: Müller Ulrich , Dörner Hans-Dieter 
Published: February 2015

Abstract
As(C6H5)4
+[Cl2H]- crystallizes in the monoclinic space group B2/b with four formula units per unit cell, the lattice constants being a =1704, 6 = 1751, c - 705 pm and y = 92.73°. The crystal structure was determined and refined from X-ray diffraction data to a residual index of R = 0.043. The Cl2H- ion is situated on an inversion center with a Cl···Cl distance of 309 pm. The IR and Raman spectra confirm the presence of symmetrical Cl2H- ions; the observed splitting of IR bands can be explained by factor group analysis. A simple procedure for the preparation consists of the reaction of HCl with As(C6H5)4Cl
Fixierung von Metallcarbonylen auf Poly-Isocyaniden [1] / Anchoring of Metal Carbonyls on Poly Isocyanides [1]
Authors: Menzel Hartmut , Fehlhammer Wolf Peter , Beck Wolfgang 
Published: February 2015

Abstract
Polyisocyanides with the groups -CH2N ≡ C and -C(O)O(CH2)2N≡C attached to polystyrene have been prepared and reacted with various metal carbonyl compounds resulting in the fixation on the polymeric supports of-M(CO)5, -M(CO)4 (M = Cr, Mo, W), -MO(Cl)(η-C5H5)(CO)2, -Mn2(CO)η -Mn(CO)ηX (N = 3, 4; X = Cl, Br), -Fe(CO)4, -Fe3(CO)11, -FeI2(CO)2, -FeX(η-C5H5)(CO) (X = Cl, Br, I), -Ru(CO)4, -Ru3(CO)9, ,,-Os3H2(CO)10", and -RhCl(CO)2. The cyano complexes [Fe(CN)2(η-C5H5)CO]- and [Mo(CN)2(η-C5H5)(CO)2]- have been immobilized by alkylation with chloromethylated polystyrene
Heteronucleare Clustersysteme, XX [1] μ3-Bi8mutio-cyclo-tris(tricarbonyliridium) (3 Ir-Ir), BiIr3(CO)9 Darstellung und Strukturuntersuehung eines neuartigen Iridiumclusters / Heteronuclear Cluster Systems, X X [1] μ3-Bismutio-cyclo-tris(tricarbonyliridium)(3Ir-Ir), BiIr3(CO)9 - Synthesis and Structural Investigation of a Novel Iridium Cluster
Authors: Kruppa Werner , Bläser Dieter , Boese Roland , Schmid Günter 
Published: February 2015

Abstract
The synthesis of BiIr3(CO)9 is described. IR and mass spectroscopic data are discussed. The structure of BiIr3(CO)9 was solved by X-ray analysis. The structural data are discussed and compared with those of the related compounds Ir4(CO)12 and Bi[Co(CO)4]3, respectively
Mesoionische Sechsringheterocyclen, IV [1]; Struktur des 2-Ferrocenyl-3.5-diphenyl-6-oxo-6H-1.3-oxazin-3-ium-4-olats / Mesoionic Six-Membered Heterocycles, IV [1] Structure of 2-Ferrocenyl-3,5-chphenyl-6-oxo-6H-l,3-oxazine-3-ium-4-olat
Authors: Debaerdemaeker Tony , Friedrichsen Willy 
Published: February 2015

Abstract
The structure of the title compound has been determined by X-ray crystallography
Mesoionische Sechsringheterocyclen, V [1, 2]; Reaktionen von 6-Oxo-6H-1.3-oxazin-3-ium-4-olaten mit o-Chinonen und Heterokumulenen / Mesoionic Six-Membered Heterocycles, V [1, 2] Reactions of 6-Oxo-6H-l,3-oxazin-3-ium-4-olates with o-Quinones and Heterocumulenes
Authors: Friedrichsen Willy , Kujath Eckard , Liebezeit Gerd 
Published: February 2015

Abstract
Mesoionic 6-oxo-6H-1,3-oxazine-3-ium-4-olates (1, 7) react with o-quinones (2, 4) to give compounds 3, 6, which may result from a primary [4+4]cycloaddition and subsequent loss of carbon dioxide. Phenyl isocyanate and phenylisothiocyanate react with 1h and 9 - possibly via a [2 + 4]cycloadduct - to give 11, 12, 13 and 14, respectively
Über die Konformation yon 1.2.4.5-Tetrathian / On the Conformation of 1,2,4,5-Tetrathiane
Authors: Susilo Rudy , Gmelin Rolf 
Published: February 2015

Abstract
The conformation of 1,2,4,5-tetrathian was determined by means of dynamic NMR spectroscopy. The barrier (ilG+) of the chair/twist equilibration is 14.5 kcal/mol and the chair form is more stable than the twist form in this molecule by 1.4 kcal/mol. These experimental data are in excellent agreement with force field calculations
Synthesen mit aliphatischen Dialdehyden, XXXII [1] Darstellung und Reaktionen N-substituierter 2-Aminomalondialdehyde / Syntheses with Aliphatic Dialdehydes, XXXII [1] Syntheses and Reactions of N-Substituted 2-Aminomalondialdehydes
Authors: Reichardt Christian , Rust Ulrich 
Published: February 2015

Abstract
The 2-amino malondialdehyde bis[dimethylacetal] 2 and some of its N-monosubstituted derivatives 7 a-d as well as the o-carboxy benzoyl malondialdehyde 12 have been prepared. With heterocyclic imonium salts these amino malondialdehyde derivatives form, by a twofold condensation reaction, the y-acylamino-substituted pentamethine cyanine dyes 15 a-c, 17, and 18a-b, the UV/Vis and 13C NMR spectra of which are recorded with respect to the influence of the y-substituent on these spectra
Triplett-sensibilisierte Isomerisierung des Insektizids Thiodan / Triplet Sensibilized Isomers of the Insecticide Thiodane
Authors: Parlar H. , Baumann R. , Bahadir M. 
Published: February 2015

Abstract
The photoisomerization reactions of cyclodiene insecticide Thiodane were investigated in different solvent systems, with wavelengths above 290 nm. The results show that /S-isomere (2) can be converted in the presence of acetone into the a-isomere (1). Photokinetic experiments give sufficient information on the character of the excited state of these compounds
Neue Silber(I)-germanate / New Silver(I)-germanates
Authors: Jansen Martin 
Published: February 2015

Four silver(I)-germanates have been prepared from the binary components Ag2O and GeO2 by solid state reaction applying elevated oxygen pressures (2500-3000 bar). Ag6Ge2O7 isisostructural to Ag6Si2O7(II) [P21,a= 16.268(3), b = 10.021(2), c = 5.320(1) Å, β = 90.85(2)°], Ag10Ge4O13 to Ag10Si4O13 [PT, a = 11.731(3), b = 9.147(3), c = 8.727(4) Å, a = 99.33(2), β = 91.61(1), γ = 114.27(2)°].
According to the results of preparative investigations and chemical analysis there are two further phases in the system Ag2O/GeO2 of compositions ′Ag2GeO3′ and ′Ag2Ge2O5′.
S4N4 und seine Derivate: Isolierung und Struktur von Pd2(S3N)2(S3N2) / S4N4 and its Derivatives: Isolation and Structure of Pd2(S3N)2(S3N2)
Authors: Thewalt Ulf 
Published: February 2015

Abstract
The reaction of S4N4 with PdCl2 in methanol yields among other products the dinuclear complex Pd2 (S3N)2(S3N2) (D): dark red needles, space group R"3̄ with a = 32.759(15), c = 6.516(4) Å and Z = 18. The structure of D was determined by an X-ray analysis. Each palladium atom is part of an almost planar PdS3N metallocycle. The SNSNS group acts as a bridge whereby each of its terminal S atoms is bonded to both Pd atoms. The Pd atoms possess a square planar coordination by four S atoms. The coordination planes form an angle of 114.9°. The Pd-Pd distance of 2.921(2) Å is rather short.
Ein methylimidoverbrücktes Diphosphoran, in dem Stickstoff nicht Glied eines Ringes ist / A Methylimido-bridged Diphosphorane in which Nitrogen is not Member of a Ring
Authors: Röschenthaler Gerd-Volker , Storzer Werner 
Published: February 2015

Abstract
N-Substituted 2-Amino-4,4,5,5-tetrakis(trifluoromethyl)-l,3,2 λ3 (λ5)-dioxaphospholanes, Dilithium Perfluoropinacolate, Diazadiphosphetidine, 2,2,2 -Trichloro -4,4,5,5 -tetrakis (trifluoromethyl) -1,3,2 λ5 -dioxaphospholane
MeN(PCl2)2 reacts with Li2[0C(CF3)2C(CF3)2O] to give MeN{P[0C(CF3)2C(CF3)2O]}2 which adds chlorine under formation of MeN{PCl2[0C(CF3)2C(CF3)2O]}2 .
The chlorophosphorane decomposes slowly to yield PCl3[0C(CF3)C(CF3)2O] and the diazadiphosphetidine {MeNPCl[OC(CF3)2C(CF3)2O]}2.
Koordinationschemie von Liganden mit den Donatoren Phosphor und Schwefel, I Nickel(II)-Komplexe mit Phosphinomethylthioethera als Liganden Gleichgewicht zwischen planarem und tetraedrischem Nickel(II) / Coordination Chemistry of Ligands with the Donors Phosphorus and Sulfur, I Nickel(II) Complexes with Phosphinomethylthioethers as Ligands A Planar-Tetrahedral Equilibrium with Nickel(II)
Authors: Gerdau Thomas , Kramolowsky Reinhard 
Published: February 2015

Abstract
The preparation and structural characterization of phosphinomethylthioethernickel(II) complexes of the general type [NiX2(Ph2PCH2SR)2] (X = CI, Br, I, NCS: R = Me, Ph) are reported. In all the complexes the phosphinomethylthioethers act as monodentate ligands coordinating via the phosphorus atom. The isothiocyanate complexes are diamagnetic both in solution and in the solid state and have been assigned trans-planar configuration. As shown by magnetic measurements and by electronic spectroscopy, the halo complexes exhibit a square-planar (diamagnetic) ⇄ distorted-tetrahedral (paramagnetic) equilibrium in solution, while in the solid state the complexes are either square-planar or distorted-tetrahedral. For the complex [NiBr2(Ph2PCH2SMe)2] both isomers have been isolated in the solid state.
Ethyldiphenylphosphin und 1.2-Bis [bis(β-diphenylpho8phinoethyl)pho8phino] ethan: Derivate des Hexacarbonyl]iydridovanadium(+I) und Hexacarbonylvanadat(—I) / Ethyldiphenylphosphine and l,2-Bis[bis(β-diphenylphosphinoethyl)phosphino]ethane: Derivatives of Hexacarbonylhydridovanadium(+I) and Hexacarbonylvanadate(—I)
Authors: Rehder Dieter , Puttfarcken Uwe 
Published: February 2015

The coordination properties of Ph2PEt (pi) and
(Ph2PCH2CH2)2PCH2CH2P(CH2CH2PPh2)2 (P2P4) towards HV(CO)6 and [V(CO)6]- are compared. Preparation and spectral properties (IR, 1H, 31P and 51V NMR) are described for the complexes HV(CO)4(p1)2, [Et4N][V(CO)6-n(p1)n] (n = 1, 2), HY(CO)mP2P4 (m = 1-5) and [Et4N][V(CO) mP2P4] (M = 1-3). The anionic species are obtained by photo-induced CO exchange, the hydrido complexes by treatment of the anionic complexes with t-BUCl/H2O or - more conveniently - by ion exchange on silica gel (m - 1-3) and subsequent UY irradiation (m = 4, 5). Complexes containing four CO groups are cis-configurated, the p1 species being extremely labile. Trisubstitution yields an isomeric mixture of mer- and fac-[V(CO)3p2p4]-. A consistent explanation of the 1H pattern in the hydride region is possible on the basis of a facecapped octahedral structure with a restricted dynamic behaviour. The positions of the CO ligands in HV(CO)3p2p4 and HV(CO)2P2P4 are facial and trans, respectively. Only chelate five-ring structures are formed.