Über Chalkogenolate. 126. Untersuchungen über N-Cyanformamidinodithiocarbimidsäure 2. Thermisches Verhalten von Kalium-N-cyanformamidinodithiocarbimat in Lösung

On Chalcogenolates. 126. Studies on N-Cyanformamidino Dithiocarbimic Acid. 2. Thermal Behaviour of Potassium N-Cyanformamidino Dithiocarbimate in Solution The thermal treatment of K₂[S₂C?N? C(NH₂)?N? CN] in methanolic solution yields . The semi-hydrate has been isolated. It reacts with acid to form The reaction with H₃CI gives The compounds have been characterized by means of electron absorption, ¹H- and ¹³C-N.M.R., infrared, and mass spectra.     

Über Chalkogenolate. 101. Untersuchungen über Halbester der Monothiokohlensäure. 1. Darstellung und Eigenschaften von Oxoxanthaten

On Chalcogenolates. 101. Studies on Hemiesters of Monothiocarbonic Acid. 1. Preparation and Properties of Oxoxanthates Alkyl oxoxanthates of alkali metals have been prepared by reaction of COS with the corresponding alkoxides. The reaction of ethyl oxoxanthate with methyl iodide leads to S-methyl-O-ethyl ester of monothiocarbonic acid. The oxidation of [SOC? OC₂H₅]^? ions with iodine forms bis(ethoxycarbonyl)-disulfide (S? CO? OC₂H₅)₂. The prepared compounds have been characterized with chemical and thermoanalytical methods as well as by means of electron absorption spectra, infrared spectra, ¹H-NMR spectra, and mass spectra.     

Über Chalkogenolate. 146. Asymmetrische Derivate der Kohlensäure mit Elementen der IV. Hauptgruppe. Notiz über Silbermonomethylcarbonat

On Chalcogenolates. 146. Asymmetric Derivatives of Carbonic Acid with main Group IV Elements. Notice of Silver Monomethyl Carbonate The esters of carbonic acid have been prepared by different methods. The compounds were characterized by means of infrared, nuclear magnetic resonance (¹H and ¹³C), and mass spectra. Synthesis and properties of unstable Ag[O₂C? OCH₃] are described. The infrared spectrum is given.     

Über Chalkogenolate. 165. Umsetzungen von Hydrazin mit Kohlenstoffdisulfid. 4. Salze des S-Methylesters der N-Dithiomethylendithiocarbazidsäure

On Chalcogenolates. 165. Reactions of Hydrazine with Carbon Disulfide. 4. Salts of the S-Methyl Ester of N-Dithiomethylene-dithiocarbazic Acid The S-methyl ester of dithiocarbazic acid reacts with carbon disulfide in the presence of sodium or potassium hydride at ?15°C to yield the hitherto unknown salts of the S-methyl ester of N-dithiomethylene-dithiocarbazic acid. The prepared compounds , have been studied with chemical methods as well as with electron absorption, infrared, nuclear magnetic resonance (¹H and ¹³C), and mass spectra.     

Über Chalkogenolate. 162. Umsetzungen von Hydrazin mit Kohlenstoffdisulfid. 1. Darstellung und Eigenschaften von 1,2-Hydrazin-bis(dithioformiaten)

On Chalcogenolates. 162. Reactions of Hydrazine with Carbon Disulfide. 1. Synthesis and Properties of 1,2-Hydrazine-bis (dithioformates) The prepared 1,2-hydrazine-bis(dithioformates) have been characterized with chemical methods as well as by means of electron absorption, infrared, nuclear magnetic resonance (¹H and ¹³C), and mass spectra.     

Zur Kenntnis der Chemie der Metallcarbonyle und der Cyanokomplexe in flüssigem Ammoniak. XXXI. Über die Reaktionen von kationischen η5-Cyclopentadienylmolybdäncarbonyl-Komplexen mit flüssigem Ammoniak

The Chemistry of Metal Carbonyls and Cyano Complexes in Liquid Ammonia. XXXI. On the Reactions of Cationic η⁵-Cyclopentadienyl-molybdenumcarbonyl Complexes with Liquid Ammonia Depending on the reaction conditions, the cationic complexes [η⁵-C₅H₅Mo(CO)₃L]⁺ (L = NH₃, PPh₃, CO) react with liquid ammonia according to: The characteristics and reactivities of the new carbomoyl derivatives are described.     

Über Chalkogenolate. 76. Untersuchungen über Glykolkohlensäuren. 1. Alkalimetallglykolmonocarbonate und -glykolidicarbonate

On Chalcogenolates. 76. Studies on Glycol Carbonic Acids. 1. Glycol Monocarbonates and Glycol Dicarbonates of Alkali Metals The reactions between CO₂ and glycolates lead to glycol carbonates. The compounds have been prepared and characterized by different methods. The i.r. spectra have been assigned.     

Über Chalkogenolate. 154. Reaktion von N-Methylformamid mit Kohlenstoffdisulfid 1. Darstellung und Eigenschaften von N-Methyl-N-formyl-dithiocarbamaten

On Chalcogenolates. 154. Reaction of N-Methyl Formamide with Carbon Disulfide. 1. Synthesis and Properties of N-Methyl N-Formyl Dithiocarbamates N-Methyl formamide reacts with carbon disulfide in the presence of sodium hydride, potassium hydroxide, and barium hydroxide to form the corresponding N-methyl N-formyl dithiocarbamate. The prepared compounds have been characterized with chemical and thermal methods as well as by means of electron absorption, infrared, nuclear magnetic resonance (¹H and ¹³C), and mass spectra.     

Organische Phosphorverbindungen XXIX. Eine neue Methode zur Darstellung von dialkylaminomethylsubstituierten Phosphonig- und Phosphinsäuren der allgemeinen Formel R2NCH2PH(O)OH und (R2NCH2)2P(O)OH [1]

A new method for the preparation of dialkylaminomethyl-phosphonous and-phosphinic acids, R₂NCH₂P(O)H(OH) and (R₂NCH₂)₂P(O)OH, is described. This involves reaction of hypophosphorous acid with hydroxymethyl-dialkyl-amines or a mixture of formaldehyde and a secondary amine. and The crystalline acids form monohydrates which are stable up to the melting points of the acids. The IR. and ³¹P-NMR. spectra are reported.     

Über Oberflächenverbindungen von Übergangsmetallen. VIII. Die Komplexbildung von koordinativ ungesättigtem Oberflächen-Chrom (II) mit Oxiden des Stickstoffs

On Surface Compounds of Transition Metals. VIII. Complex Formation of a Coordinatively Unsaturated Cr^II Surface Compound with Nitrogen Oxides N₂O forms with surface-Cr(II) a relatively unstable light blue compound of the stoichiometry 1:1, while addition of NO results in formation of a very stable dark brown, diamagnetic surface complex . By reaction with O₂ this complex undergoes — depending on reaction temperature — either replacement of NO unter reoxidation of the metal (→Cr(VI)) or/and reaction of the ligand (→NO₂). Direct reaction of NO₂ with results in the same products as stepwise addition of NO and 1/2 O₂. reacts with HCl/ROH under formation of the soluble, paramagnetic kation [Cr(NO)(ROH)_n]²⁺, which is formulated as [Cr(II)(NO)]²⁺ ? [Cr(I)(NO⁺)]²⁺ accordingly to the e.s.r. spectra.     

Zur Thermodynamik der Metallcarbonate 3. Mitteilung [1]. Löslichkeitskonstanten und Freie Bildungsenthalpien von ZnCO3 und Zn5(OH)6(CO3)2 bei 25°

The solubilities of ZnCO₃ and Zn₅(OH)₆(CO₃)₂ have been investigated at 25°C in solutions of the constant ionic strength 0,2 M consisting primarily of sodium perchlorate. From experimental data the following values for equilibrium constants and GIBBS free energies of formation are deduced: A predominance area diagram for the ternary system Zn²⁺–H₂O–CO_2(g) including ZnO, ZnCO₃, Zn₅(OH)₆(CO₃₎₂, and Zn²⁺ is given.     

A shock tube study of H + HNCO → NH2 + CO

The reaction of atomic hydrogen with isocyanic acid (HNCO) to produce the amidogen radical (NH₂) and carbon monoxide, has been studied in shock-heated mixtures of HNCO dilute in argon. Time-histories of the ground-state NH₂ radical were measured behind reflected shock waves using cw, narrowlinewidth laser absorption at 597 nm, and HNCO time-histories were measured using infrared emission from the fundamental v₂-band of HNCO near 5 μm. The second-order rate coefficient of reaction (2(a)) was determined to be: cm³ mol^?1 s^?1, where f and F define the lower and upper uncertainty limits, respectively. An upper limit on the rate coefficient of was determined to be:      

Kinetic investigation of the bromate–ascorbic acid–malonic acid system

According to our experiments the bromide ion concentration exhibits in the bromate–ascorbic acid–malonic acid–perchloric acid system three extrema as a function of time. To describe this peculiar phenomenon, the kinetics of four component reactions have been studied separately. The following rate equations were obtained: Bromate–ascorbic acid reaction: Bromate–bromide ion reaction: Bromide–ascorbic acid reaction: Bromine–malonic acid reaction: k₄ = 6 × 10^?3 s^?1, k_-4 ≥ 1.7 × 10³ s^?1, k₅ ≥ 1 × 10⁷M^?1 · s^?1 Taking into account the stoichiometry of the component reactions and using these rate equations, the concentration versus time curves of the composite system were calculated. Although the agreement is not as good as in the case of the component reactions, it is remarkable that this kinetic structure exhibits the three extrema found.     

Über die oxidative Fluorierung von (CF3)(R) (R = CF3, Cl) und die Kristallstruktur von (CF3)(Cl)F+ AsF6−

Oxidative Fluorination of (CF₃)(R) (R = CF₃, Cl) and the Crystal Structure of (CF₃)(Cl) F⁺ AsF₆^? Oxidative fluorination of (CF₃)(R) (R = CF₃, Cl) with XeF⁺MF₆^? (M = As, Sb) in anhydrous HF results in formation of monofluorsulfonium hexafluorometalates. The salts are characterized by vibrational, NMR, and mass spectra. (CF₃)(Cl)F⁺ AsF₆^? crystallizes in the monoclinic space group P2₁/c with a = 9.955(10) Å, b = 11.050(5) Å, c = 12.733(15) Å, β = 97.77(5)°, and Z = 4.     

Über Chalkogenolate. 171. Reaktion von N,N′-Diphenylformamidin mit Kohlenstoffdisulfid 4. Ester der N,N′-Diphenyl-N-formimidoyldithiocarbamidsäure

On Chalcogenolates. 171. Reaction of N,N′-Diphenyl Formamidine with Carbon Disulfide. 4. Esters of N,N′-Diphenyl-N-Formimidoyl Dithiocarbamic Acid Potassium N,N′-diphenyl N-formimidoyl dithiocarbamate reacts with alkyl halides to yield the corresponding esters \documentclass{article}\pagestyle{empty}\begin{document}${\rm C}_6 {\rm H}_5 {\rm N} = CH - {\rm N}({\rm C}_6 {\rm H}_5) - {\rm CR} - {\rm SR, where R = CH}_3,{\rm C}_2 {\rm H}_5,{\rm CH}_2 - {\rm C}_6 {\rm H}_5,$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}${\rm and (C}_6 {\rm H}_5 {\rm N} = CH - {\rm N}({\rm C}_6 {\rm H}_5) - {\rm CS)}_{\rm 2} = {\rm CH}_2 .$\end{document} The phenyl ester (R = C₆H₅) has been synthesized by reaction of N,N′-diphenyl formamidine with the phenyl ester of chlorodithioformic acid. The prepared compounds have been characterized by means of electron absorption, infrared, nuclear magnetic resonance (¹H and ¹³C), and mass spectra.     

Über Chalkogenolate. 99. Untersuchungen über Monothiocarbamidsäure 1. Darstellung und Eigenschaften von Monothiocarbamaten

On Chalcogenolates. 99. Studies on Monothiocarbamic Acid. 1. Synthesis and Properties of Monothiocarbamates The monothiocarbamates , and Ba[SOC? NH₂]₂ have been prepared and characterized by means of infrared, electron absorption, and mass spectra. The existence of the free monothiocarbamic acid was ascertained.     

Tetramethyldisilan-1,2-diyl-verbrückte Dicyclopentadienyl-und Diindenylmetalldichloride der 4. Gruppe – Kristallstruktur von

Tetramethyldisilane-1,2-diyl bridged Dicyclopentadienyl and Diindenyl Metal Dichlorides of the Group 4 Metals – Crystal Structure of Dicyclopentadienyl and diindenyl metal dichlorides of the type Cp′? SiMe₂SiMe₂? Cp′MCl₂ (Cp′ = C₅H₄, M = Ti ( 1 ), Zr ( 2 ), Hf ( 3 ); Cp′ = C₉H₇, M = Zr ( 4 ), Hf ( 5 )) were synthesized and characterized by means of their ¹H, ¹³C, ²⁹Si-n.m.r., MS, and IR spectra. The crystal structure of 2 was determined.     

Täuschend einfache 1H-NMR-Spektren bei symmetrisch aufgebauten,zwei Phosphoratome enthaltenden organischen Verbindungen

The ¹H-NMR spectra of symmetric compounds with two phosphorus atoms of the type R? X? P? Y? P? X? R, R = CH₃, C₂H₅, X = —, O, NCH₃, NCH₂—, Y = NCH₃, have been determined. After elimination of eventual couplings within the alkyl protons these spectra always show triplets in the case of trivalent phosphorus and doublets in the case of pentavalent phosphorus atoms. Since this paper establishes an unequal coupling between the alkyl protons and the two phosphorus nuclei, it is concluded that these compounds show a degenerate, however deceivingly simple, coupling: The spectra of symmetric diorgano diphosphines can be interpreted via the same mechanism. Calculations to substantiate these findings are reported.     

Über Chalkogenolate. 121. Untersuchungen über N-Cyanomonothiocarbimidsäure 1. Darstellung und Eigenschaften von Alkalimetall-N-cyanomonothiocarbimaten

On Chalcogenolates. 121. Studies on N-Cyanomonothiocarbimic Acid. 1. Synthesis and Properties of Alkali Metal N-Cyanomonothiocarbimates The hitherto unknown N-cyanomonothiocarbimates M₂[SOC?N? CN] · H₂O, where M = Na, K, Rb, Cs, have been prepared by reaction of the corresponding alkali metal salt of cyanamide with COS. N-Cyanomonothiocarbimates react with sulfur to form the ion, which gives with an acid and with CH₃I the methyl compound . The reaction of the latter compound with H₂O₂ yields . All compounds have been characterized by means of diverse methods.     

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.