Übergangsmetallchalkogenverbindungen. Über CuNH4WS4 und Cu2WS4 und andere Übergangsmetallchalkogenmetallate

Transition metal chalkogen compounds. On CuNH₄WS₄, Cu₂WS₄ and other transition metal chalkogenometallates The preparation, vibrational and electronic spectra of CuNH₄WS₄, Cu₂WS₄ and other transition metal compounds, which could not be isolated in a pure form, are reported. The X-ray data of CuNH₄WS₄ are given.     

Über die Natur der Übergangsmetall-Kohlenstoff-σ-Bindung. VIII. Über die Reaktion von 3d-Metallhalogeniden mit Thioanisolyllithium

On the Nature of the Transition Metal Carbon-σ-Bond. VIII. Reaction of 3d-Metal Halides with Thioanisolyl Lithium Reaction of CoBr₂ · 2 THF with PhSCH₂Li/N(CH₂CH₂)₃N (TED) results in the formation of the thiophenolato complex LiCo(SPh)₃ · TED · 3.5 THF (I) with ethylene, propylene, and small amounts of cyclopropane being liberated. The constitution of I follows from the results of the elemental analysis, the effective magnetic moment (μ_eff. = 4.41 B.M.), and the reaction with acids and HgCl₂ to give PhSH and PhSHgCl, respectively. I could also be isolated by comparison synthesis from CoBr₂ · 2 THF and LiSPh/TED. Other 3d-metal halides MX_n · xTHF (M = Ti, V, Mn, Fe, Ni; X = Cl, Br) also react very easily with thioanisolyl lithium to form thiophenolato compounds.     

Übergangsmetallphosphidokomplexe. VII. Ringgrößeneffekte bei den NMR-Daten von Übergangsmetallphosphor-Vier- und Sechsringkomplexen

Transition Metal Phosphido Complexes. VII. Ring Size Effects within the N.M.R. Data of Transition Metal Phosphorus Four- and Six-membered Ring Complexes Comparing the corresponding n.m.r. data of [cpNiPH₂]₂ 1 and [cpNiPH₂]₃ 2 , of [(CO)₄MnPH₂]₂ 3 and [(CO)₄MnPH₂]₃ 4 , and of [(CO)₄MnPF₂]₂ 5 and [(CO)₄MnPF₂]₃ 6 , respectively, it is shown that mainly the coupling constant between the phosphorus nuclei J_PMP (M = Ni, Mn) and all chemical shift values are strongly influenced by the ring size. The relevant coupling constants between the nuclei ¹H, ³¹P, and ¹⁹F have been obtained using computer simulations of the corresponding higher order spin systems.     

Über neue Bufadienolide aus Ch'an Su. Über Krötengifte, 34. Mitteilung

Two new bufadienolides, isolated from Ch'an Su, are proved to be 19-oxo-cinobufagin (III) and 19-oxo-cinobufotalin (V), respectively.     

Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. XXXII. Über Benzylverbindungen des Kupfers

Contributions to the Chemistry of Transition Metal Alkyl Compounds. XXXII. On Benzyl Copper Compounds Benzyl copper is formed reacting copper dichloride or acetylacetonate with dibenzyl zinc complexed by chlorides or acetylacetonates of copper and zinc. The complexes decompose between ?15 and +25°C with separation of copper and benzyl radicals proved by spin trap experiments. The stability of the compound is not influenced remarkably by substituents in o-position but is caused by complex formation with triphenyl phosphine. Pure benzyl copper, obtained by decomposition of BzCu · 0.25 BzZn(acac) · 0.75 Zn(acac)₂ by means of diethyl ether, decomposes spontaneously even at a temperature of ?50°C.     

Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. XL. Über Lithium-alkenylmanganate(II)

Contributions to the Chemistry of Transition Metal Alkyl Compounds. XL. About Lithium Alkenylmanganates(II) MnCl₂ reacts with vinyl, 2,2-dimethylvinyl, allyl, and methallyl lithium giving rise to alkenyl manganates(II). In a pure state the compounds Li₂[Mn(CH?CH₂)₄] · 1.5 diox, Li₂[Mn(CH?C(CH₃)₂)₄] · 1.5 diox, Li₂[Mn(CH₂? CH?CH₂)₄] · 2.5 diox and Li₃[Mn(CH₂? C(CH₃)?CH₂)₅] · 2 diox were isolated. The compounds were characterized by elementary analysis, EPR and IR spectra, magnetic moments, and reactions with iodine.     

Über Chalkogenolate. LXX. Versuche zur Darstellung von Tetrathiooxalaten Über Alkylthio-1,3-dithiol-2-thione

On Chalcogenolates. LXX. Experiments to Prepare Tetrathiooxalates. About Alkylthio-1,3-dithiol-2-thiones Experiments to prepare tetrathiooxalates have been described. The electrolytic reduction of carbon disulfide and the reaction of sodium with CS₂ lead to formation of C₃S₅^2? ions beside others. The alkylations of C₃S₅^2? give alkylthio-l,3-dithiol-2-thiones. The formation of polymeric tetrathiooxalates has not been proved.     

Über Rubidiumozonid. Reindarstellung und Kristallstruktur

On Rubidium Ozonide. Synthesis and Crystal Structure An improved route for the synthesis of rubidium ozonide is reported. Via repeated ozonization of the hyperoxide at room temperature and extraction with liquid ammonia, pure rubidium ozonide is for the first time available in preparative amounts (1–5 g) and moreover as single crystals. The crystal structure determination (P2₁/c; a = 645.2(3), b = 602.2(3), c = 876.3(3) pm, ß 122.34(2)°; ?20°C; MoKα 2640 diffractometer data; R_w = 2.6%) proves the expected constitution of the anion O₃^?, which within the range of error belongs to the point group C_2v with d (O? O) = 133.6(9) pm and a bonding angle of 113.7(7)°. With respect to the packing of cations and anions there is a close relationship to the CsCl-type of structure.     

Über Trichlorphosphazo-Verbindungen aus Nitrilen. I

The compound [HCCl=C(NPCl₃)(PCl₃)[PCl₆], VI, is formed in the reaction between acetonitrile and PCl₅. Reaction of H₂S with VI results in the formation of the chloride and by further reactions of this chloride with BCl₃ and SbCl₅ the tetrachloroborate and hexachloroantimonate salts respectively, are obtained. Chloroacetonitrile can be made to react with PCl₅ to give HCCl?C(NPCl₃)Cl, II, by use of suitable conditions. There is no indication that mixtures of cis/trans isomers of VI or II exist as has been previously postulated. The ¹H and ³¹P NMR spectra of the above-mentioned compounds and numerous further products from the reactions of CH₃CN, ClCH₂CN and Cl₂CHCN with PCl₅ are discussed in detail. II occurs in a cisoid and a transoid conformation.     

Über Chalkogenolate. 201. Untersuchungen über Selenformamide

On Chalcogenolates. 201 Studies on Selenoformamides The yellow selenoformamides H? CSe? NH₂, H? CSe? NH? CH₃, and H? CSe? N(CH₃)₂ have been prepared by reaction of the corresponding formamide with P₂Se₅. The compounds have been characterized by means of electron absorption, infrared, and nuclear magnetic resonance spectra. The decomposition of the selenoformamides in ethanolic solution has been studied kinetically at 20.0°C. The preparation of selenoformyl dithiocarbamates was not successful.     

Über Phosphorstickstoff-Verbindungen. XXXI. Über neue viergliedrige Ringsysteme mit Stickstoff,Phosphor und Kohlenstoff im Ring

A P? N compound XI, formula see ?Inhaltsübersicht”?, has been prepared containing three interconnected four-membered rings. On chlorination of XI P₂(NCH₃)₂Cl₆ is re-formed, besides a further product being very probably compound XII with hexa-coordinated phosphorus. Interaction between the known Cl₄P(NCH₃)₂ CCl₂ and NN′-dimethyl urea yields III and another compound, VII, with phosphorous of coordination number six.     

Über Chalkogenolate. 86. Massenspektren von Dialkyltrithiocarbonaten

On Chalcogenolates. 86. Mass Spectra of Dialkyl Trithiocarbonates Dialkyl trithiocarbonates have been studied by means of mass spectra. The decomposition schemes are communicated.     

Über Chalkogenolate. 145. Trimethylgermanyl- und Trimethylstannylcarbonate

On Chalcogenolates. 145. Trimethylgermyl and Trimethylstannyl Carbonates The hitherto unknown salts of the hemiesters of carbonic acid Li[O₂C? OGe(CH₃)₃] and Li[O₂C? OSn(CH₃)₃] have been prepared by reaction of Li[OGe(CH₃)₃] and Li[OSn(CH₃)₃], respectively, with CO₂ at 0°C. Both compounds were characterized by means of diverse spectoscopic methods.