Über Chalkogenolate. 81. Untersuchungen über N-Hydroxydithiocarbamidsäure 3. Ester der N-Hydroxydithiocarbimidsäure und -carbamidsäure

On Chalcogenolates. 81. Studies on N-Hydroxy Dithiocarbamic Acid. 3- Esters of N-Hydroxy Dithiocarbimic Acid and Dithiocarbamic Acid The reaction between hydroxylamine, carbon disulfide, and alkyl halide leads to the corresponding ester of N-hydroxy dithiocarbimic acid HO? N?C(SR)₂ with R = CH₃, C₂H₅; R₂ = ? CH₂? CH₂? . The phenyl ester of N-hydroxy dithiocarbamic acid HO? NH? CS(SC₆H₅) has been prepared by reaction of hydroxylammonium chloride with the phenyl ester of chlorodithioformic acid. N-Methyl hydroxylammonium chloride reacts with carbon disulfide and alkyl iodide to form the corresponding ester of the dithiocarbamic acid HO? N(CH₃)? CS(SR) with R = CH₃, C₂H₅. The unstable compounds have been characterized by different methods.     

Über Chalkogenolate. 122. Untersuchungen über N-Cyanomonothiocarbimidsäure 2. Kalium-S-methyl-N-cyanomonothiocarbimat und S-Methyl-N-cyanomonothiocarbimidsäure

On Chalcogenolates. 122. Studies on N-Cyanomonothiocarbimic Acid. 2. Potassium S-Methyl N-Cyanomonothiocarbimate and S-Methyl N-Cyanomonothiocarbimic Acid The reaction of K₂[SOC?N? CN] · H₂O with H₃CI gives K[O(H₃CS)C?N? CN]. The potassium salt reacts with acid to form (HO)(H₃CS)C?N? CN and with H₃CO? CO? Cl to yield (H₃CO? CO? O)(H₃CS)C?N? CN. The compounds have been characterized by means of spectroscopic methods.     

Über Chalkogenolate. 128. Untersuchungen über Ester der N-Cyancarbamidsäure. 1. Darstellung und Eigenschaften der Ammoniumsalze von N-Cyancarbamidsäureestern und vom N-Methyl-N-cyancarbamidsäureethylester

On Chalcogenolates. 128. Studies on Esters of N-Cyancarbamic Acid. 1. Synthesis and Properties of Ammonium Salts of N-Cyancarbamic Acid Esters and of the Ethyl Ester of N-Methyl N-Cyancarbamic Acid The reaction of NC? N(CO? OR)₂ with NH₃(g) yields NH₄[NC? N? CO? OR], where R = CH₃, C₂H₅, and C₆H₅. NH₄[NC? N? CO? OC₂H₅] reacts with H₃CI to form NC? N(CH₃)? CO? OC₂H₅. The called compounds have been studied with chemical and spectroscopic methods.     

Über Chalkogenolate. 123. Untersuchungen über N-Cyanomonothiocarbimidsäure. 3. O,S-Dimethylester der N-Cyanomonothiocarbimidsäure. Thiolyse und Hydrolyse des Esters

On Chalcogenolates. 123. Studies on N-Cyanomonothiocarbimic Acid. 3. O, S-Dimethyl Ester of N-Cyanomonothiocarbimic Acid. Thiolysis and Hydrolysis of this Ester (H₃CO)(H₃CS)C?N? CN has been prepared by reaction of K₂[SOC?N? CN] · H₂O with H₃CI. The thiolysis of this ester gives (H₃CO)(H₃CS)C?N? CS? NH₂. The acid hydrolysis forms (H₃CO)(H₃CS)C?N? CO? NH₂ via [(H₃CO)(H₃CS)C?N? C?NH]Cl. All compounds have been characterized by diverse methods.     

Kationen mit Xenon—Kohlenstoff-Bindung. 4. Salze mit monosubstituiertem Phenylxenon-Kation: Darstellung,Stabilität und Reaktivität

Cations with Xenon-Carbon Bonds. 4 Salts with Monosubstituted Phenyl Xenon Cation: Preparation, Stability and Reactivity . Nucleophilic fluorine aryl substitution reactions with monosubstituted phenylboranes (X? C₆H₄)₃B and fluorophenylboranes (X? C₆H₄)_nBF_3?n (n = 1 and 2; X = m-F, p-F, m-CF₃ and p-CF₃) on XeF₂ lead to the formation of [X? C₆H₄Xe]⁺ salts with arylfluoroborate anions [(X? C₆H₄)_nBF_4?n]^? (n = 2, 1 and 0). Their thermal behaviour, their spectroscopic properties and first investigations concerning their reactivity are reported.     

Über Chalkogenolate. 135. Untersuchungen über Ester von Halogenoameisensäuren 3. Darstellung und Charakterisierung von Fluoro- und Bromothioameisensäurealkylestern

On Chalcogenolates. 135. Studies on Esters of Haloformic Acids. 3. Synthesis and Characterization of Alkyl Esters of Fluoro- and Bromothioformic Acid ⁿC₃H₇S? CO? F, C₂H₅S? CS? F, and ⁿC₃H₇S? CS? F have been prepared by reaction of the corresponding chloro compound with KF by use of phase transfer catalysts. The esters RS? CS? Br, where R ? C₂H₅ and ⁿC₃H₇, are formed by reaction between RSH and SCBr₂ in the presence of pyridine. The compounds have been characterized by means of diverse spectroscopic methods.     

Über Chalkogenolate. 93. Untersuchungen über Trithioallophansäure 2. Darstellung und Eigenschaften der freien Säure [1]

On Chalcogenolates. 93. Studies on Trithioallophanic Acid 2. Preparation and Properties of the Free Acid Yellow trithioallophanic acid H₂N? CS? NH? CS(SH) has been prepared by reaction between a suspension of K[S₂C? NH? CS? NH₂] in diethyl ether and a solution of HCl in (C₂H₅)₂O at ?15°C; the ether was distilled off at ?15°C in vacuo. The compound has been characterized by means of infrared spectra, electron absorption, ¹H-NMR spectra, and mass spectra. The dissociation constant of trithioallophanic acid in water is K_a = (1,41 ± 0,08) · 10^?2 at 20°C.     

Über Chalkogenolate. 94. Untersuchungen über Trithioallophansäure 3. Ester der Trithioallophansäure [1]

On Chalcogenolates. 94. Studies on Trithioallophanic Acid. 3. Esters of Trithioallophanic Acid. The esters of trithioallophanic acid H₂N? CS? NH? CS(SR) with R = CH₃, CH₂C₆H₅ have been characterized by means of electron absorption spectra, infrared spectra, ¹H NMR spectra, and mass spectra.     

Über Chalkogenolate. 151. Untersuchungen über Derivate der N-Thioformyldithiocarbamidsäure. 1. Darstellung und Eigenschaften von N-Thioformyldithiocarbamaten

On Chalcogenolates. 151. Studies on Derivatives of N-Thioformyl Dithiocarbamic Acid. 1. Synthesis and Properties of N-Thioformyl Dithiocarbamates The N-thioformyl dithiocarbamates M[S₂C? NH? CS? H], where M = K, Rb, Cs, Tl, NH₄, [N(ⁿC₄H₉)₄], Na[S₂C? NH? CS? H] · 0.5 H₂O, and Ba[S₂C? NH? CS? H]₂ · 3 HO? CH₂? CH₂? OCH₃ have been prepared by use of partial different procedures. The compounds were characterized with chemical and thermal methods as well as by means of electron absorption, infrared, nuclear magnetic resonance (¹H and ¹³C), and mass spectra. Attempts to synthesize N-thioformyl dithiocarbamic acid were not successful.     

Über Chalkogenolate. 139. Untersuchungen über Dialkylester von Chalkogenokohlensäuren. 2. O,Se- und S,Se-Dialkylmonothiomonoselenocarbonate

On Chalcogenolates. 139. Studies on Dialkyl Esters of Chalcogenocarbonic Acids. 2. O,Se- and S, Se-Dialkyl Monothiomonoselenocarbonates The hitherto unknown esters RSe? CS? OR′, where R = C₂H₅, ⁿC₃H₇ and R′ = C₂H₅, ⁿC₃H₇, are formed by reaction of NaSeR with Cl? CS? OR′ and of RSe? CS? Cl with HOR′. At the first time, the esters RSe? CO? SR′ with R = R′ = C₂H₅, ⁿC₃H₇ have been prepared by reaction between NaSeR and Cl? CO? SR′. The compounds have been characterized by means of diverse spectroscopic methods.     

Über Chalkogenolate. 137. Isothiocyano-, Isothiocyanomonothio- und Isothiocyanodithio- ameisensäurealkylester

On Chalcogenolates. 137. Alkyl Esters of Isothiocyanoformic, Isothiocyanomonothioformic and Isothiocyanodithioformic Acids The esters RO? CO? NCS, where R = CH₃, C₂H₅, as well as RS? CO? NCS and RS? CS? NCS with R = C₂H₅, ⁿC₃H₇ have been prepared by three different methods. The reaction between the corresponding chloro compound and KSCN in the presence of the phase transfer catalyst 18-crown-6 gives the highest yields. The electron absorption, infrared, nuclear magnetic resonance, and mass spectra of these compounds are reported.     

Über Chalkogenolate. 152. Untersuchungen über Derivate der N-Thioformyldithiocarbamidsäure. 2. Kristallstruktur von Tetra-n-butylammonium-N-thioformyldithiocarbamat

On Chalcogenolates. 152. Studies on Derivatives of N-Thioformyl Dithiocarbamic Acid. 2. Crystal Structure of Tetra-n-butylammonium N-Thioformyl Dithiocarbamate The title compound [N(ⁿC₄H₉)₄][S₂C? NH? CS? H] crystallizes with Z = 2 in the triclinic space group P1 with cell dimensions a = 9.694(2) Å, b = 11.478(3) Å, c = 12.551(6) Å, α = 63.03(3)°, β = 66.42(2)°, γ = 85.60(2)°. The crystal structure has been determined from single crystal X-ray data measured at 20°C and refined to a conventional R of 0.061 for 2249 independent reflections (R_w = 0.042). The structure is built up of dimeric aggregates consisting of 2[N(ⁿC₄H₉)₄]⁺ cations and 2[S₂C? NH? CS? H]^? anions. The two anions are linked together by ? CS? S…?H? N bridges. To make possible a space saving stacking of the dimeric aggregates in the crystal, one methyl group in terminal position of one n-butyl chain in the cation has gauche conformation.     

1,2-Bis-triphenylphosphoranylidenamino-äthan als zweizähniger Ligand in Übergangsmetallkomplexen

1,2-Bis-(triphenylphosphorane-ylidene-amino)ethane as a Bidentate Ligand in Transition Metal Complexes The reactions of Ph₃P?N? C₂H₄? N?PPh₃ with transition metal halogenides MX₂ give according to eq. (1) novel bisiminophosphorane complexes of the type M(Ph₃PNC₂H₄ NPPh₃)X₂ (M ? Co, X ? Cl 1 a , Br 1 b , J 1 c ; M ? Ni, X ? Cl 2 a , Br 2 b , J 2 c , M ? Hg, X ? Cl 3 , M ? Cd, X ? Cl 4 ). The preparation, properties, magnetic moments, and structure of the new complexes are reported     

Über Chalkogenolate. LVII. Untersuchungen über Thioameisensäuren 5. Darstellung und Eigenschaften von Estern der Dithioameisensäure

Esters of the trimeric dithioformic acid [HCS(SR)]₃ were prepared by interaction of K[HCS₂] with alkyl iodides (R = CH₃, C₂H₅). Orthoesters HC(SR)₃ and di-orthoesters of the monomeric dithioformic acid were formed by reaction of formic acid with thioles (RSH mit R = CH₃, C₂H₅, CH₂C₆H₅) or dithioles (HS? (CH₂)_n? SH with n = 2, 3,4). The prepared compound were characterised by different methods.     

Phosphinsubstituierte Chelatliganden. XVIII. Penta- und Tetracarbonylmetall-Komplexe des Chroms,Molybdäns und Wolframs mit sekundären und tertiären Phosphinothioformamid-Liganden

Phosphine Substituted Chelate Ligands. XVIII. Penta- and Tetracarbonylmetal Complexes of Chromium, Molybdenum, and Tungsten with Secondary and Tertiary Phosphinothioformamide Ligands Mono- and bidentately coordinated phosphinothioformamide complexes are obtained by photochemical substitution of the metal hexacarbonyls M(CO)₆ (M ? Cr ( a ), Mo ( b ), W ( c )). The M(CO)₅ · THF adducts react with secondary thioamides under exclusion of light to give the P-coordinate pentacarbonyl complexes [(CO)₅MPPh₂C(S)NHR¹] (R¹ ? Ph ( 1a – c ), Me ( 2a )). The photoreaction of M(CO)₅ · THF with secondary and tertiary thioamides at low temperatures leads to the formation of the P, S-chelate complexes . The corresponding N-silylated complexes 6a – c (R¹ ? Me₃Si, R² ? Ph) are obtained by direct photosubstitution of M(CO)₆ in cyclohexane solution. The labile bis(thioformamide) complexes [(CO)₄M(PPh₂C(S)NHMe)₂] ( 7a – c , cis-trans isomers) are synthesized in low yields according to the same procedure. The attempted alkylation of the chelate complexes 3a – c remains unsuccessful, whereas the secondary thioformamides react with n-BuLi/CH₂Br₂ to give the methylene bis(thioformirnidoesters) [Ph₂PC(NR¹)S]₂CH₂ (R¹ ? Ph (8), Me ( 9 )) in quantitative yields.     

Über Chalkogenolate. 202. Derivate der Selendithioallophansäure 1. Synthese und Charakterisierung von Selendithioallophanaten

On Chalcogenolates. 202. Derivatives of Selenodithioallophanic Acid. 1. Synthesis and Characterization of Selenodithioallophanates The hitherto not known, dark red colored selenodithioallophanate K[S₂C? NH? CSe? NH₂] has been prepared by reaction of K₂[S₂C?N? CN] with H₂Se and characterized by means of electron absorption, infrared, and nuclear magnetic resonance spectra.     

Aminomethylierung von Thiophosphorsäuredialkylester-, Phosphon- bzw. Thiophosphonsäurealkylesteramiden,Phosphon- bzw. Thiophosphonsäurediamiden und Diphenylthiophosphinsäureamid

Aminomethylation of Phosphoro-, Phosphono-, Phosphinoamidoates and -amidothioates Dialkylphosphoroamidates, alkyl-phosphonoamidates and phosphonoamidothioates react with C₂H₅O? CH₂? NR₂ and HCOH/HNR₂, respectively, as like as a N-aminomethylation forming the corresponding derivatives of the general formula R₂P(X)? NR′? CH₂? NR″₂? R = alkoxy, alkyl, aryl; R′ = H, alkyl; X = O, S; R″ = alkyl, cycloalkyl —. Under the same conditions phosphonodiamidoates and phosphonodiamidothioates yield RP(X)-[NR′? CH₂? NR″₂]₂ or RP(X)? NHR′? (NR′? CH₂? NR″₂) only. These compounds are not formed by interactions of RP(X)(NR′? CH₂OH)₂ with sec. amines. The aminomethylation of (C₆H₅)₂P(S)NH₂ gives unexceptional [(C₆H₅)₂P(S)]₂N? CH₂? NR′₂. The i.r. and ¹H-n.m.r. data of the prepared compounds, which can't be distilled mostly, are discussed.     

Über Chalkogenolate. 134. Untersuchungen über Ester von Halogenoameisensäuren 2. Darstellung und Eigenschaften von Se-Alkylestern der Chloromonothiomonoselenoameisensäure [1]

On Chalcogenolates. 134. Studies on Esters of Haloformic Acids 2. Synthesis and Properties of Se-Alkyl Esters of Chloromonothiomonoselenoformic Acid The hitherto unknown esters RSe? CS? Cl with R ? C₂H₅ and ⁿC₃H₇ have been prepared by reaction of thiophosgene with the corresponding alkane selenol. The compounds have been characterized with electron absorption, nuclear magnetic resonance (¹H, ¹³C, and ⁷⁷Se), infrared, and mass spectra.     

Strukturen ladungsgestörter oder räumlich überfüllter Moleküle. 15. Tetracyanethen-Natrium-Dimethoxyethan

Structures of Charge-Perturbed or Sterically Overcrowded Molecules. 16. Tetracyanoethylene Sodium Dimethoxyethane The Single crystal structure of [(NC)₂C? C(CN)₂?·Na⊕(H₃CO? CH₂CH₂? OCH₃)]∞ reveals two formula units within the triclinic (P1 ) unit cell. The tetracyanoethylene radical anions are arranged along parallel double layers, which are shifted relative to each other, and in between which are interspersed the sodium counter cations and their dimethoxyethane ligands. The distances within the double layers amount to 300 pm and the ones between them to 385 pm. The six-fold coordinated Na⊕ centers are surrounded by four radical anions with contact distances Na…?N between 250 and 254 pm as well as by a twofold solvent ligand with Na…?O of 238 and 241 pm. Due to the electron transfer to the acceptor molecule, its (NC)₂C-halves twist by 8° and the bond lengths of the N?C? C subunits, bent by each 3°, are shortened up to 2 pm. The structural parameters are compared to those of the analogous potassium salt [TCNE^?K^⊕DME], of the dianion , of the sodium salts [(NC)₃C^?Na^⊕]∞ as well as [(NC)₂C? C(CHCH)₂? C(CN)₂^?Na^⊕]_∞ and, in addition, are discussed based on geometry-optimized MNDO calculations.     

Über Chalkogenolate. 85. Untersuchungen über Halbester der Trithiokohlensäure 3. Schwingungsspektren von Alkylthioxanthogensäuren und Wasserstoffbrücken in den freien Säuren

On Chalcogenolates. 85. Studies on Hemiesters of Trithiocarbonic Acid 3. Vibrational Spectra of Alkyl Thioxanthic Acids and Hydrogen Bondings in the Free Acids The IR spectra of alkyl thioxanthic acids RS? CS(SH) with R = CH₃, C₂H₅, ⁿC₃H₇, ⁱC₃H₇, ⁿC₄H₉, ^sC₄H₉, ^tC₄H₉, and CH₃S? CS(SD) as well as the Raman spectrum of the Compound with R = CH₃ have been assigned. The formation of hydrogen bondings in the free acids has been studied by means of i.r. spectra, ¹H-n.m.r. spectra, and electron absorption spectra. The energies of the hydrogen bondings have been calculated.