Nitrosyl-Metallkoordinationsverbindungen. VI. Synthese und Eigenschaften von Cobalt- und Eisenkomplexen des Typs M(S,S)(P,P)NO

Nitrosyl Metal Coordination Compounds. VI. Syntheses and Properties of Cobalt and Iron Complexes of the Type M(S,S)(P,P)NO Penta-coordinated neutral complexes of the composition M(S,S)(P,P)NO, with M = Co, Fe; S,S = malonitrildithiolate (mnt), P,P = tetraphenylethylenediphosphine (diphos), and triphenylphosphine (PPh₃) have been synthesized and investigated by means of molecular weights measurement, IR, UV/VIS, and ESCA spectroscopy as well as magnetic measurements. Square pyramidale and trigonal bipyramidale structures are discussed.     

Darstellung und Eigenschaften von Komplexen des Typs cis-(RCN)3M(CO)3 (M = Cr,M, W)

Metal complexes of the type cis-(RCN)₃M(CO)₃ (M = Cr, Mo, W) have been prepared by different methods starting with M(CO)₆ or, more conveniently, with substituted derivatives of the metal hexacarbonyls. Infrared spectroscopic studies indicate that the strength of the nitrile-to-metal bond in cis-(RCN)₃M(CO)₃ is only sligthly influenced by the R group. The chromium compounds cis-(RCN)₃Cr(CO)₃ may be used as starting materials for the preparation of hexaalkylborazine-chromium-tricarbonyls.     

Metall-Pseudohalogenide. XXXIX. Dicyanamid-Komplexe von Palladium(II) und Platin(II) des Typs M{N(CN)2}2L2

Metal Pseudohalides. XXXIX. Dicyanamide Complexes of Palladium(II) and Platinum(II) of the Type M{N(CN)₂}₂L₂ The synthesis of mixed dicyanamide complexes of the type M{N(CN)₂}₂L₂ (M: Pd, Pt) is reported. Infrared and NMR-spectroscopic investigations are indicating the hitherto undescribed coordination type M? N(CN)₂ of the anionic ligand.     

Synthese und Struktur von Hydrogensulfaten des Typs M(HSO4)(H2SO4) (M = Rb,Cs und NH4)

Synthesis and Structure of Hydrogen Sulfates of the Type M(HSO₄)(H₂SO₄) (M = Rb, Cs and NH₄) From the binary systems M₂SO₄/H₂SO₄ (M = Rb, Cs, NH₄), three new hydrogen sulfates of the type M(HSO₄)(H₂SO₄) could be synthesized and structural characterized. The rubidium and caesium compounds are isotypic whereas NH₄(HSO₄)(H₂SO₄) is topologically very similar to both. All three compounds crystallize with nearly identical cell parameters [Rb: a = 7.382(1), b = 12.440(2), c = 7.861(2), β = 93.03(3); Cs: a = 7.604(1), b = 12.689(2), c = 8.092(2), β = 92.44(3); NH₄: a = 7.521(3), b = 12.541(5), c = 7.749(3), β = 92.74(3)], in the monoclinic space group P2₁/c, There exist two kinds of SO₄-tetrahedra: HSO₄^? anions (S1) and H₂SO₄-molecules (S2). The HSO₄^? anions form hydrogen bridged zigzag chains. In the case of the Rb and Cs compounds, the H₂SO₄ molecules connect these chains forming double layers. The metal atoms are coordinated by 9 O-atoms with M? O-distances of 2.97 – 3.39 Å (Rb) and 3.13 – 3.51 Å (Cs). In the ammonium compound additional hydrogen bonds are formed originating from the NH₄⁺ cation. This finally leads to the formation of S2? NH₄⁺ chains (parallel to the S1 chains) as well as to a three-dimensional connection of both kinds of chains.     

Synthese,Kristallstruktur und Eigenschaften von Vanadium(II)‐tetrachloroaluminat

Synthesis, Crystal Structure, and Properties of Vanadium(II) Tetrachloroaluminate The reaction of vanadium dichloride and aluminium trichloride yields vanadium(II) tetrachloroaluminate. Amber cuboid crystals can be obtained by slow cooling of the melt. V(AlCl₄)₂ crystallizes in the monoclinic space group I2/c (a = 1284.6(3), b = 776.3(2), c = 1163.5(2) pm, β = 92.376(10)°) and is therefore isotypic to Co(AlCl₄)₂. The structure contains chains build of VCl₆ octahedra and AlCl₄ tetrahedra sharing corners and edges with each other. The temperature dependence of the magnetic susceptibility follows Curie‐Weiss behaviour (μ = 3.88(2) μ_B, Θ = ?9(1) K) complying with the spin‐only paramagnetism expected of d³ ions.     

Zur Synthese von Molekularsieben des Typs X aus Kaolinen,Tonen und Kraftwerksfilteraschen

Ohne Zusammenfassung     

Synthese,Kristallstruktur und Eigenschaften von Phosphor(V)-nitridimid HP4N7

Synthesis, Crystal Structure, and Properties of Phosphorus(V) Nitride Imide HP₄N₇ Pure HP₄N₇ was obtained as a fine crystalline solid which is resistant to hydrolysis. The compound was synthesized by thermal condensation at 750 °C in sealed quartz ampoules starting from the molecular precursor compound (NH₂)₂P(S)NP(NH₂)₃. The crystal structure was solved by direct methods and refined by a Rietveld algorithm on the basis of synchrotron X-ray powder diffraction data which have been collected at the NSLS Brookhaven, beamline X7A (HP₄N₇, P2₁/a, a = 1507.95(2), b = 480.304(6) c = 710.722(8)pm, β = 92.191(1)°, Z = 4, 1689 reflections, wR_p = 0.082, R_p = 0.063, R_F = 0.038). In HP₄N₇ there are PN₄-tetrahedra as characteristic structural motifs which are connected through common edges and corners resulting in a three-dimensional network structure. Two out of seven nitrogen each are bridging two and the remaining N are bridging three neighbouring P atoms. Solid state IR spectroscopy of HP₄N₇ reveals a strong N–H stretching vibration at 3089 cm^–1. The ³¹P MAS NMR spectrum shows one signal at –26 ppm. In a nonoxidizing atmosphere HP₄N₇ is stable up to 800 °C. Above that temperature NH₃ eliminates and P₃N₅ is formed.     

Synthese,Eigenschaften und Struktur von cis-Dihydridoazido-tris(triphenylphosphino)-iridium

Synthesis, Properties, and Structure of cis-Dihydrido Azido Tris(triphenylphosphino) Iridium cis-IrH₂(N₃)(PPh₃)₃ is formed from IrCl₃(PPh₃)₃ and NaN₃ in alcohol. The solvent transfers the hydride ions whereby aldehyde is formed. The creme-colored cis-IrH₂(N₃)(PPh₃)₃ is a diamagnetic low-spin complex. Exposure to light yields H₂ and Ir(N₃)(PPh₃)₃ in a reversible process. The cis position of the hydrido ligands is confirmed by the i.r. and H-N.M.R. spectra. Cis-IrH₂(N₃)(PPh₃)₃ crystallizes in the monoclinic system with the space group P2₁/c. The crystal structure exhibits isolated octahedral complexes, in which one hydrido ligand is located trans to the azido group. The other one being trans to one of the phosphine ligands.     

ESR-Untersuchungen zu Struktur- und Bindungsverhältnissen von tri- und bicyclischen Cobalt(II)- und Kupfer(II)-Chelaten mehrzähniger Schiffscher Basen des Typs M(O N N O) und M(S N)2 sowie zur Sauerstoffadduktbildung der Cobalt(II) Chelate

Structural and Bonding Properties of Quadridentate and Bidentate Cobalt(II) and Copper(II) Schiff Base Complexes and Oxygenation Behavior of the Co^II Complexes. An ESR Study ESR investigations on the low-spin cobalt(II) chelates bis(benzoylacetaldehyde)-ethylendiimine-cobalt(II), bis(benzoylacetaldehyde)-1,2-cyclohexandiimine-cobalt(II) and bis(p-chlor-β-mercaptozimtaldanilato)-cobalt(II) as well as the corresponding copper(II) chelates are reported. The large anisotropy of the g tensor of the Co^II chelates caused by strong spin-orbit interactions, and the position of the maximum g tensor component g_x in the molecules obtained by comparison with the ESR spectra of the Cu^II complexes predicts a MO for the unpaired electron which consists mainly of the Co d_yz obital. In solution (CHCl₃/pyridine) the Co^II chelates react immediately with molecular oxygen forming [CoL_n(O₂)(py)] species characterized by ESR spectra with strongly reduced g tensor anisotropy and small ⁵⁹Co hyperfine coupling constants. The unpaired electron appears to be mainly localized in the O₂-part of hte molecules. The CoN₂S₂ coordination sphere shows a lower affinity to oxygen than the CoN₂O₂ type complexes. In the CuN₂O₂ complexes the unpaired electron is found to be in a MO containing the Cu d_xy orbital. Due to remarkable covalency¹⁴ N and H hyperfine interactions are observed in the ESR spectra. Analyzing the hyperfine coupling constants the extent of unpaired spin density on the N donor atoms and the N-2s/2p hybridization degree is estimated.     

Synthese und Eigenschaften von Bis(Dimethylarsino)-aminen

Synthesis and Properties of Bis(dimethylarsino) Amines Primary amines react with cacodyl halides (CH₃)₂AsX (X = Cl, J) under formation of Bis(dimethylarsino)amines RN[As(CH₃)₂]₂. Nine amines were prepared. The compounds were characterized by IR, ¹H-nmr and mass-spectroscopy. In the reactions with acid molecules cleavage of the As? N bond was observed. Formation of amine RNH₂ or ammoniumsalt (RNH₃)X and cacodyl derivates took place in all cases. The reactions of the arsinoamines with some carbonyles are reported.     

Synthese und Eigenschaften von Bis(dialkylamino)-methylarsinen

Synthesis and Properties of Bis(dialkylamino)methylarsines The reactions of secondary amines with CH₃AsJ₂ lead to the formation of Bis(dialkylamino)methylarsines. Ten arsines have been prepared by this method and are described. IR and ¹H-NMR and mass spectral data are presented for these compounds and discussed. Acid molecules cleave the As? N bond. The reactions with halogen hydrides, water, alkoholes, thioles and amines are described.     

Synthese und dielektrische Eigenschaften des 9-Acridinaldehyd-Acetals und des 3-Pyrenaldehyd-Acetals von Polyvinylalkohol

Ohne Zusammenfassung     

Darstellung und Eigenschaften von 3-(N,N-Dimethylamino)propyl-Verbindungen des Thalliums

Preparation and Properties of 3-(N,N-Dimethylamino)propyl Thallium Compounds TlCl₃ reacts with Me₂NCH₂CH₂CH₂Li in molar ratio 1:2 with formation of (Me₂NCH₂CH₂CH₂)₂TlCl ( 1 ) which can be transfered with MeLi into (Me₂NCH₂CH₂CH₂)₂TlMe ( 2 ) and with excess of Me₂NCH₂CH₂CH₂Li into (Me₂NCH₂CH₂CH₂)₃Tl ( 3 ) respectively. Comproportionation of 1 with TlCl₃ yields rather instable Me₂NCH₂CH₂CH₂TlCl₂ ( 4 ) from which Me₂NCH₂CH₂CH₂TlMe₂ ( 5 ) can be obtained by alkylation with MeLi. 1–3 and 5 were characterized by elemental analysis, mass spectra, ¹H- and ¹³C-n.m.r. spectra.     

Synthese,Eigenschaften und Kristallstrukturen von Magnesium-Diazadien-Komplexen

Synthesis, Properties and Crystal Structures of Magnesium Diazadiene Complexes Reactions of phenyl-substituted 1,4-diaza-1,3-butadienes (DAD) RN?CPh? CPh?NR (R = C₆H₅) 1a , C₆H₄-4-CH₃ 1b , C₆H₄-4-OCH₃ ( 1c ) with magnesium in dimethoxyethan lead to complexes of the type [Mg(DAD)₂(DME)] 2a–c , with DAD ligands in form of radical anions. Furthermore, highly reactiv complexes of the composition [Mg(DAD)(DME)₂] 3a–c could be obtained. The crystal structures of 2a, 3a and 3c were determined.     

Synthese,Eigenschaften und Kristallstruktur des cis-Dichloro-bis(diethyldithiophosphinato)titan(IV)

Synthesis, Properties, and Crystal Structure of cis-Dichloro-bis(diethyldithiophosphinato)-titanium(IV) By reaction of TiCl₄ with dialkyldithiophosphinic acids R₂P(S)SH (R ? CH₃, C₂H₅) red chelates (R₂PS₂)₂TiCl₂ are obtained which are very sensitive to hydrolysis. Crystal structure analysis of the ethyl compound shows a distorted octahedral chromophor TiS₄Cl₂ with cis-configuration.     

Darstellung und Eigenschaften von Disilanderivaten des Typs Si2 me 4 X 2

Derivatives of DisilanesXme ₂SiSime ₂ X withX=H, F, Cl, Br, J, Ome, Ph, Sme, and Si₂ me ₅Sme were prepared, some of them for the first time, and investigated by spectroscopic methods. The hitherto unknown group of sulphur compounds of disilanes show similarities with the corresponding polysilane (Si _n me _2n+2,n=Si+S) in their UV-, IR and Raman spectra, resulting from the similar mass of sulphur and silicon.     

Die Synthese und einige Eigenschaften von Hydraziniumfluoroscandaten(III)

The synthesis of N₂H₅ScF₄·0.5 HF·0.5 H₂O, N₂H₅ScF₄, and N₂H₆ScF₅ is described. The thermal properties and infrared spectra of the compounds obtained are discussed. The assignation of the bands in infrared spectra (4000 to 250 cm^?1) of the first two compounds is consistent with the presence of hydrazinium⁺¹ ion and for the third one with the presence of hydrazinium⁺² ion.     

Synthese von neuen Morphin-Teilstrukturen des Typs 15,16-Secomorphinan

Synthesis of New Morphine Partial Structure 15,16-Secomorphinan The synthesis of a new morphine partial structure, 15,16-secomorphinan, is described. One of the series, (±)-15, 16-secocyclorphan (5) , has the analgesic potency of morphine and exhibits good binding to the opiate receptor.