Zum Einfluß der Ringgröße auf die Struktur von Metallchelaten dreizähliger Liganden. II.; Stabilitätsmessungen an Chelaten pyridylsubstituierter Dialkylsulfide mit 3d-Elementen

Inhaltsübersicht. Es wird über die Komplexbildung zwischen Ionen der 3d-Elemente und Bis[β-pyridyl(2)-äthyl]-sulfid (3, 3-py₂S-tri) und [Pyridyl(2)-methyl]-[β-pyridyl(2)-äthyl]-sulfid (2, 3-py₂S-tri) in wäßriger Lösung berichtet. 2, 3-py₂S-tri bildet mit Kupfer(ii)- und Nickel(ii) 1, 1- nnd 1,2-Komplexe, in denen es als dreizähliger Ligand fungiert. In den Komplexen M(2,3-py₂S-tri-H)³⁺ (M = Cu(II) oder Nickel(ii)) besetzen die Liganden 2,3-py₂S-tri-H⁺'zwei Koordinationsstellen und bilden Chelatfünfringe aus. Bei dem Liganden 3,3-py₂S-tri konnten normale und protonierte 1,1-Komplexe, im Falle des Kupfer(II) auch ein 1,2-Komplex nachgewiesen werden. Für eine Komplexbildung zwischen Kobalt(ii) oder Zink(ii) und 2,3-py₂S-tri oder 3,3-py₂S-tri ergaben sich keine Hinweise. Aus sterischen Gründen sind die Komplexe des stärker basischen Liganden 3,3-py₂S-tri instabiler als die des 2,3-py₂S-tri. The Influence of Ring Size on the Structure of Metal Chelates with Tridentate Ligands. II. Stability Measurements of 3d-Metal Chelates with Pyridyl Substituted Dialkyl Sulfides Abstract. The complex formation between ions of the 3d-elements and bis[β-pyridyl(2)-ethy)]-sulfide (3,3-py₂S-tri) and [pyridyl(2)-methyl]-[β-pyridyl(2)-ethyl]-sulfide (2,3-py₂S-tri) was investigated in aqueous solution. 2,3-py₂S-tri forms 1,1- und 1,2-complexes with copper(II) and nickel(ii) acting as a tridentate ligand. In the complexes M(2,3-py₂S-tri-H)³⁺ (M = Cu(ii) or Ni(ii)) the ligand 2,3-py₂S-tri-H⁺ is bidentate forming a five-membered chelate ring. With the ligand 3,3-py₂S-tri normal and protonated 1,1-complexes were detected, in the case of copper(ii) also a 1,2-complex. No complex formation was observed between cobalt(ii) or zinc(ii) and 2,3-py₂S-tri or 3,3-py₂S-tri. From steric reasons the complexes of the higher basic ligand 3,3-py₂S-tri are more instable than the those of the ligand 2,3-py₂S-tri.     

Untersuchungen über die reaktionsfähigkeit von chrom und titan mit pyrrolidindithiocarbaminat

The dependence of the reactivity with pyrrolidinedithio-carbamate of titanium on pH and the presence of other ions, and of chromium^III on the state of binding of the chromium^III ion and on pH have been investigated. The results of this investigation provide an explanation of the hitherto very variable accounts of the reactivity of titanium and chromium with disubstituted dithiocarbamates.

Résumé

Les auteurs étudient l'influence du pH et de la la présence d'autres ions sur le pyrrolidinedithiocarbamate de titane et l'influence du pH et de l'état sous lequel se trouve le chrome (III) en solution sur le pyrrolidinedithiocarbamate de chrome (III). Les résultats obtenus permettent d'expliquer les différences rencontrées quant aux réactions du chrome et du titane avec les dithiocarbamates bisubstitués.     

Metallkomplexe mit anionischen Liganden von Elementen der 4. Hauptgruppe. VII. Über das Substitutionsverhalten von Carbonylnitrosyl-und Nitrosyltrifluorphosphin-Übergangsmetallkomplexen gegenüber Trichlorstannid-Ionen

Metal Complexes with Anionic Ligands of Elements of the Main Group IV. VII(¹) Substitution Reactions of Carbonylnitrosyl and Nitrosyltrifluorophosphine Transition Metal Complexes with Trichlorostannid L-substitution by [SnCl₃]^? occurs if the nitrosyl complexes Co(NO)L₃ and Fe(NO)₂L₂ (L = CO or PF₃) are reacted with [N(C₂H₅)₄][SnCl₃] thermically in tetrahydrofuran as well as photochemically induced in methylenechloride. The complexes Co(NO)L₃ yield the mono-substitution products [N(C₂H₅)₄][Co(NO)L₂SnCl₃], with the iron compounds Fe(NO)₂L₂ only the disubstituted derivative [N(C₂H₅)₄]₂[Fe(NO)₂(SnCl₃)₂] can be isolated. On the other hand CO substitution at (π-C₅H₅)Mo(NO)(CO)₂ by UV irradiation did not suceed both with [SnCl₃]^? and with PF₃. From the IR-spectroscopic data a leastly with PCl₃ comparable π-acceptor ability is derived for the trichlorostannido ligand.     

Zum komplexchemischen Verhalten von potentiell vier- und fünfzähligen Bis(salicylidenamino)-Liganden gegenüber Ionen der 3d-Elemente

Studies on the Coordinative Behaviour of Potentially Four and Fivedentate Bis(salicylidene amino)-Ligands with Ions of the 3d-Elements. Fourdentate bis(salicylidene amino)-ligands (^?ONΦCH₂ΦNO^? and ^?ONΦOΦNO^?, meaning of the abbreviations see text) with the centres of donor atoms connected by rigid, bifunctional residues, form polymeric complexes Me^II(ONΦCH₂ΦNO) and Me^II(ONΦOΦNO) with cobalt(II), nickel(II), and copper(II). Among the cobalt(II) chelates the structure is uniformly tetrahedral, but the nickel(II) and copper(II) complexes contain square planar central atoms and such with a higher coordination number side by side. The potential fivedentate ligands ^～ON3PPh3NO^?, ^?ON2O2NO^?, and ^?ON2S2NO^? differ as to their coordinative behaviour. The coordination number of the complexes Ni(ON3PPh3NO) and Co(ON3PPh3NO) is five. On the other hand the compounds Co(ON2S2NO) and Co(ON2O2NO) are tetrahedral. No coordination of the ether or sulfide group is observed. Ni(ON2O2NO) has an octahedral structure which is produced by coordination polymerisation and possibly by coordination of the ether group. The new complexes are compared with the transition metal complexes of simple salicylaldimines.     

Über Tellurhalogenide des Kupfers mit hoher lonen-Teilleitfähigkeit. III. Zur Phasenumwandlung von CuTeBr und zur Struktur der Hochtemperaturphase

Telluride Halides of Copper with High Ionic Partial Conductivity. III. On the Phase Transition of CuTeBr and the Structure of the High Temperature Phase Copper telluride bromide, CuTeBr, exhibits a reversible sudden change of the electric conductivity. From caloric data a first order phase transition at 345 K can be concluded with ΔH_u = 76.8 cal/g-mol and ΔS_u = 0.222 cal/g-mol K. X-ray measurements show a sudden change of the lattice parameters and the disappearance of the — orthorhombic — superstructure at the transition. Single crystal determinations of the HT-phase yield the tetragonal main structure (space group I 4₁/amd); simultaneously a rearrangement of the statistical population of the Cu sites is observed. The results are discussed on the basis of a displacive transition.     

Zinn(IV)-Komplexe mit dreizähnigen diaciden Liganden — 119Sn-NMR und 119mSn-Mössbauer-spektroskopische Untersuchungen

Tin(IV) Complexes with Tridentate Diacidic Ligands — ¹¹⁹Sn NMR and ^119mSn Mössbauer Studies The tin(IV) chelates of tridentate diacidic azomethines of acetylacetone resp. salicylaldehyde with benzoylhydrazine, thiobenzoylhydrazine, 2-hydroxyaniline and 2-mercaptoaniline as well as with the ligands 2-(2′-hydroxy-4-methylphenyl)-6-(2″-hydroxyphenyl)pyridine, 2-(2′-hydroxyphenyl)-8-quinolinol and 2.6-diphenacylpyridine were synthesized. The compounds were characterized by IR-, UV/VIS-, MS-, ¹¹⁹Sn NMR and ^119mSn Mössbauer spectroscopy. They exist as a mixture of geometrical isomers.     

Beiträge zur Chemie der Silicium-Stickstoff-Verbindungen. 163. Untersuchungen über einige Verbindungen mit BNSi-Struktureinheiten

Chemistry of Silicon-Nitrogen Compounds. 163. Investigation of Some Compounds with BNSi Structure Fragments Some formerly unknown compounds with BNSi structure fragments were prepared (or obtained on a not expected way), confirmed in their structure and described in their properties: (EtO)₂BN(SiMe₃)₂ ( V ), FB[N(SiCl₃)₂]₂ ( XIII ), the derivatives IV, XVI – XIX of the six-, five- and four-membered ring systems cyclotriazatriborane, cyclodisilaboradiazane, and cyclosilaboradiazane and XXIII of a [3, 4]-spiro system. Br₂BN(SiMe₃)₂ ( III ), already known, was prepared by a different method.     

Untersuchungen der Zersetzungsgleichgewichte und zur Phasenbreite der Molybdäntelluride

Investigation of Decomposition Equilibria and the Phase Fields of Molybdenum Tellurides The Te₂-pressure over Mo₃Te₄ and MoTe₂ as well as over equilibrium mixtures of Mo+Mo₃Te₄, Mo₃Te₄+MoTe₂, and MoTe₂+Te.l, respectively, has been measured directly between 1100 and 1373 K. No remarkable deviations from stoichiometry exist for MoTe₂ as well as for Mo₃Te₄. The coexistence pressures are for Mo/Mo₃Te₄: lg p/10⁵ Pa = 5.56—9879/T, and for Mo₃Te₄/MoTe₂: lg p/10⁵ Pa = 8.398—11790 /T. Third law enthalpies are derived: Δ_fH°(298, Mo₃Te₄) = —195.5±10 with S°(298) = 268, and Δ_fH°(298, αMoTe₂) = —89.5 ± 11 with S°(298) = 115.3 (values in kJ/mol and J mol^?1 K^?1, respectively).     

Metallkomplexe mit anionischen Liganden von Elementen der 4. Hauptgruppe. IX. Zum komplexchemischen Verhalten von Trichlorstannid-und Trichlorgermid-Ionen gegenüber Komplexen von Übergangsmetallen in niedrigen Oxydationsstufen

Metal Complexes with Anionic Ligands of the Main Group IV Elements. IX. Reactions of Trichlorostannide and Trichlorogermide Ions with Complexes of Transition Metals in Low Oxidation States Carhonyl trichlorostannido- and carbonyl trichlorogermido-metalate complexes have been synthesized both by photochemical and thermical substitution reactions of [ECl₃]^? ions (E = Sn, Ge) with M(CO)₆, (M = Cr, Mo, W), Fe(CO)₅ Fe₃(CO)₁₂, Co₂(CO)₈, as well as with the metalcarbonyl derivatives (π-arene)M(CO)₃, (M = Cr, Mo), (h⁵-C₅,H₅,)V(CO)₄, Mn(CO)₅,Cl, Co(NO)(CO)₃, and Fe(NO)₂,(CO)₂. Mainly the bonding properties of the [ECl₃]^? ligands are discussed by means of i.r. spectroscopic investigations. The progress of the reactions and the necessary reaction conditions show that the nucleophilic properties oft both anions [ECl₃]^? are unexpectedly small. The slightly weaker hasicity of [SnCl₃]^? compared with [GeC1₃]^? arreared, when both anions were reacted with Co₂,(CO)₈, forming the substitution product. [Co₂,(CO)₇,SnCl₃]^? and the products of a “base reaction” Cl₃GcCo(CO)₄, and [Co(CO)₄]^?.     

Über Chalkogenolate. LV. Untersuchungen über Thioameisensäuren. 3. Darstellung und Eigenschaften der Dithioameisensäure

Amorphous trimeric dithioformic acid has been prepared by interaction between an aqueous solution of K[HCS₂] and HCl(aq). After 1/2 – 1 minutes, the polymeric acid [ HCS(SH)]_X precipitates from a clear yellow solution of [HCS(SH)]₃ in N,N-dimethyl formamide or dimethyl sulfoxide. In solution (HCCl₃, H₂CCl₂), the existence of monomeric dithioformic acid has been verified. In the gaseous state [HCS(SH)]_n exists with n = 1, 2, 3. The dithioformic acid was investigated by different methods.     

Über Chalkogenolate. 153. Untersuchungen über Derivate der N-Thioformyldithiocarbamidsäure 3. Ester der N-Thioformyldithiocarbamidsäure und Oxydation von N-Thioformyldithiocarbamaten

On Chalcogenolates. 153. Studies on Derivatives of N-Thioformyl Dithiocarbamic Acid. 3. Esters of N-Thioformyl Dithiocarbamic Acid and Oxidation of N-Thioformyl Dithiocarbamates The esters of N-thioformyl dithiocarbamic acid have been prepared by reaction of tetra-n-butylammonium N-thioformyl dithiocarbamate with the corresponding alkyl iodide. Also the reaction of S-methyl N-formyl dithiocarbamate with Lawesson reagent forms the methyl ester of N-thioformyl dithiocarbamic acid. The oxidation of N-thioformyl dithiocarbamates with iodine yields 1,2,4-dithiazole-3-thione All compounds have been characterized by means of chemical and diverse spectroscopic methods. A new method to prepare 5-phenyl 1,2,4-dithiazole-3-thione is given.     

Untersuchungen zur Struktur von 1,1-Komplexen der Nickelhalogenide mit N-substituierten Aminomethyl- und Aminoäthylpyridinen

The 1.1-complexes formed by the reaction of nickel(II) halides and substituted aminoethyl- and aminomethyl-pyridines-(2) may be divided into two groups. Compounds, which are yellow or red brown in the solid state, and violet in solution in acetone belong to the first group. The complexes of the second group are violet in solution and in the solid state. On account of the vis- and ir-spectra, the magnetic behaviour, and the molar weight a distorted tetrahedral structure is discussed for the violet compounds, and a dimeric structure with coordination number 5 of the central atom for the complexes of the first group. The factors determining the structure of the investigated compounds are stated.     

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.     

Methode zur Konstitutionsaufklärung der Reaktionsprodukte der Umsetzung von Cellulose mit Formaldehyd. 18. Mitteilung über textilchemische Untersuchungen [1]

(1) A method is described which allows the elucidation of the structure of cotton cross-linked with formaldehyde. It consists of a permethylation process (5 methylations with dimethyl sulphate and sodium hydroxide in dimethyl sulphoxide, followed by two exchange methylations of the formalised sodium cellulosate with methyl iodide in n-butanol), hydrolysis of the product in 72% sulphuric acid to the respective methylated glucoses, reduction of the mixture of glucoses to the respective sorbitols, blocking of all free hydroxyl groups by acetylation, trifluoroacetylation or formation of trimethylsilyl ethers, and vapour phase chromatographic separation of the derivatives. (2) It is shown that after permethylation practically no free hydroxyl groups can be detected and that scarcely any replacement of methylene or oxymethylene cross-links by methyl groups has taken place. With the exception of losses in filtration of the permethylation product, all stages of the process proceed on an almost quantitative basis.     

Über die Dicyanierung der 1,4-Diaminoanthrachinone und die Reaktivität der 1,4-Diamino-9,10-dihydroanthracen-2,3-dicarbonitrile gegenüber nucleophilen Reagenzien 3. Mitteilung über Arylierungen und Heterocyclisierungen von Anthrachinonsystemen

The Dicyanation of 1,4-Diaminoanthraquinones and the Reactivity of 1,4-Diamino-9,10-dioxo-9,10-dihydroanthracene-2,3-dicarbonitriles towards Nucleophilic Reagents The reaction of 1-amino-9, 10-dioxo-4-phenylamino-9,10-dihydroanthracene-2-sulfonic acid ( 1 , R?C₆H₅) with cyanide in water yields a mixture of 1-amino-9,10-dioxo-4-phenylamino-9,10-dihydroanthracene-2-carbonitrile ( 3 , R ? C₆H₅) and 1-amino-4-(phenylamino)anthraquinone ( 4 , R ? C₆H₅) under the usual reaction conditions (Scheme 1). In dimethylsulfoxide, however, a second cyano group is introduced, and 1-amino-9,10-dioxo-4-phenylamino-9,10-dihydroanthracene-2,3-dicarbonitrile (7) is formed (Scheme 2). The cyano groups are very reactive towards nucleophiles. The cyano group in 2-position can be substituted by hydroxide and aliphatic amines (Schemes 5 and 6). The cyano group in 3-position can be eliminated by aliphatic amines and hydrazine (Scheme 7). Nucleophilic attack at the cyano C-atom of the 2-cyano group by suitable reagents leads to ring formation, yielding e.g. 2-(Δ²-1, 3-oxazolin-2-yl)-, 2-(benz[d]imidazol-2-yl)- and 2-(1H-tetrazol-5-yl)anthraquinones (Schemes 8 and 10).     

Cyanato-Kupfer(II)-Komplexe mit organischen Liganden. VI. Darstellung,Elektronen- und Infrarotspektren einiger Cyanato-Kupfer(II)-Komplexe mit Liganden der Anilingruppe

Cyanato-Copper(II) Complexes with Organic Ligands. VI. Preparation, Electronic and Infrared Spectra of Some Cyanato-Copper(II) Complexes with Ligands from Aniline Group Complexes of the type Cu(NCO)₂L₂ were prepared (L see “Inhaltsübersicht”), and their electronic spectra in the solid state and in solution, as well as their infrared spectra were recorded. The spectral results indicate that these complexes have — except Cu(NCO)₂(o-Tol)₂ – trans planar Cu(NCO)₂ L₂ molecules with the cyanate groups bonded through the nitrogen atom. In acetone and methanol solutions these molecules are completed with two solvent molecules to form pseudooctahedral species with different axial distortion. The complex Cu(NCO)₂(o-Tol)₂ displays bridging N-coordinated cyanate groups and thus a polymeric structure. In the acetone, methanol and chloroform solution does it exhibit no coordinated solvent molecules. The complexes with L = m- and p-toluidin in the chloroform solution are revealed as planar Cu(NCO)₂L₂ molecules.