Zur Oxydation von Nickel(0)-Komplexen mit Halogenverbindungen des Kobalt(II), Kupfer(II) und Zink(II)

Oxidation of Nickel(0) Complexes by Halogen Compounds of Cobalt(II), Copper(II), and Zine(II) In aceton as a solvent Ni(PPh₃)₄ is oxidized by; cobalt(II) complexes of the type (Ph₃P)₂CoX₂ to nickel(I) compounds. In the case of X = Cl (Ph₃P)₃NiCl and (Ph₃P)₃CoCl separately crystallize, while for X = Br the lattice compound CoNi(PPh₃)₆Br₂ and for X = I CoNi(PPh₃)₅I₂ are formed. CuBr₂ and Ni(PPh₃)₄ react to (Ph₃P)₂NiBr and (Ph₃P)_nCuBr. With (Ph₃P)₂ZnCl₂ also (Ph₃P)₃NiCl is formed But in this case the oxidant is hydrogen chloride originating from hydrolysis. The magnetic moments of the new compounds were measured and their vis and fir spectra compared with those of the simple compounds (Ph₃P)_nNiX (n = 2, 3) and (Ph₃P)₃CoX. The M–X stretching frequencies are assigned. The cobalt (I) complexes (Ph₃P)₃CoCl have identical (distorted tetrahedral) structures, but most probably the nickel (I) complexes have not.     

Potentiometrische Untersuchungen an Cu(II)- und Ni(II)-Komplexen mit gemischten Liganden

Potentiometric evidences have been cited for the formation of 1∶1∶1 ternary complexes in the systems: Cu(II)/Ni(II)-glycine-diamines [where diamines = ethylenediamine (en), propylenediamine (pn), o-phenylenediamine (phenen) and 1.8-naphthalenediamine (naphen)].     

Der Einflu? von methyl- und dimethylsubstituierten Pyridinen als Liganden auf die Struktur und den Elektronentransfer bei Thiocyanat-Kupfer(II)-Komplexen

Complexes of the type Cu(NCS)₂ L ₂ whereL are all isomeric picolines and lutidines, as well as those of the type Cu(NCS)₂ L ₃ forL=-, -picoline, 3,4-, and 3,5-lutidine were prepared. The complexes were studied by means of thermal decomposition, and by electronic andESR spectroscopy. The results obtained have been brought into correlation with the effect of the ligandsL being caused by the methyl groups on the pyridine ring. It has been found that the differences in the properties studied which appear between Cu(NCS)₂ L ₂ and Cu(NCS)₂(pyridine)₂ are conditioned especially by the steric effect of the ligandsL with the methyl group in -position. The other ligandsL, however, show also an influence on some properties of the respective complexes.     

Synthese und Antitumoraktivität voncis-Dichloroplatin(II)-Komplexen mit Östradiolderivaten

Summary Estrogen-receptor binding moieties were introduced into Pt(II) complexes in order to facilitate the selective transport into cancer cells. Estradiol esters of 2,3-diaminopropionic acid and estradiol ethers of 1,2-diamino-2-methyl-3-(p-hydroxyphenyl)propane were attached to Pt(II) complexes. The antitumor activity of the compounds was tested towards the human mammary carcinoma cell lines MDA-MB 231 and MCF-7, respectively, and the estrogen-receptor binding affinity of the Pt(II) complexes was determined. The steroidal Pt(II) complexes gave a maximum growth inhibition of 80% and a maximum estrogen-receptor binding affinity of 5.18.

     

Der Einfluß von methyl- und dimethylsubstituierten Pyridinen als Liganden auf die Struktur und den Elektronentransfer bei Thiocyanat-Kupfer(II)-Komplexen

Complexes of the type Cu(NCS)₂ L ₂ whereL are all isomeric picolines and lutidines, as well as those of the type Cu(NCS)₂ L ₃ forL=-, -picoline, 3,4-, and 3,5-lutidine were prepared. The complexes were studied by means of thermal decomposition, and by electronic andESR spectroscopy. The results obtained have been brought into correlation with the effect of the ligandsL being caused by the methyl groups on the pyridine ring. It has been found that the differences in the properties studied which appear between Cu(NCS)₂ L ₂ and Cu(NCS)₂(pyridine)₂ are conditioned especially by the steric effect of the ligandsL with the methyl group in -position. The other ligandsL, however, show also an influence on some properties of the respective complexes.

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Mit 2 Abbildungen     

Doppelkomplexsalze des Thioharnstoffs und der Thiocyanat-Ionen mit den Übergangsmetallen Cd(II), Cu(II) und Co(II)

Three new double complex compounds with the following compositions were obtained:[Cd(thio)₄]·[Cd(SCN)₄],[Cd(thio)₄]·[Co(SCN)₄], [Cu(thio)₄] [Cd₂(SCN)₆].Some of their physical properties including melting points and electric conductivity have been determined. The study of their IR-spectra shows that the metal-thiourea bond in the complex cation is formed via the sulphur atom. The Co-SCN bond in the complex anion [Co(SCN)₄]^2– is formed through the nitrogen atom, and in [Cd(SCN)₄]^2– the cadnium-thiocyanate bond is probably formed with some groups through the sulphur atom, and with others through the nitrogen.In the complex anion [Cd₂(SCN)₆]^2– the IR spectral data show that a bridging bond is also formed.     

Untersuchung von Kobalt(II)-Komplexen mit N-Arylthioharnstoffen

The complexes of cobalt(II) chloride with o, m, p-tolyl thiourea (I–III); m, p-nitrophenyl thiourea (IV, V); o, m, p-hydroxy phenyl thiourea (VI–VIII); m, p-bromophenyl thiourea (IX, X); p-iodophenyl thiourea (XI) and o-bromo-p-methyl phenyl thiourea (XII) have been synthesised. The elemental analysis reveals that ligands (I–V) form bis and the rest forms tris complexes with cobalt(II). Infrared and farinfrared spectral measurements prove that sulphur is taking part in co-ordination. All complexes are nonelectrolytes in acetone as revealed by conductivity measurements. The data obtained from magnetic susceptibility measurements, electronic spectra in solution are consistant with a practically tetrahedral symmetry.     

Komplexe des m-Methylbenzamidoxims mit Co(II) und Ni(II)

The complex formation of Co²⁺ and Ni²⁺ with m-methyl benzamide oxime was studied spectrophotometrically in 60% methanol. The complexes [Co(mMB)₂] and [Ni(mMB)₂] appear in alkaline solution. The formation constants are lgK=4.15±±0.04 for [Co(mMB)₂] and lgK=4.08±0.04 for [Ni(mMB)₂] at 25°. The decadic molar extinction coefficients are ε=5000 for [Co(mMB)₂] and ε=560 for [Ni(mMB)₂], resp.     

Synthese und Charakterisierung von Sulfinato-Nickel(II)-Komplexen

Synthesis and Characterization of Sulfinato-Nickel(II) Complexes Synthesis and properties of sulfinato-nickel(II) complexes of the type L₂Ni(Cl)SO₂R (L₂ = TMED, bipy, phen, DPPE, (PBu₃)₂; R = Ph, p-Tol, Me, NMe₂) are described. The compounds obtained are characterized by means of magnetic measurements, i.r. and reflectance spectra.     

Untersuchungen an 1,2-Komplexen der Nickel(II)-halogenide mit N-substituierten Aminoäthylpyridinen-(2)

In the solid state complexes of the type MiL₂X₂ (L = N-substituted β-aminoethyl-pyridine; X = Cl, Br, J) have a cis-octahedral (X = Cl, Br) or a distorted trigonal bipyramidal structure (X = J). In solutions in acetone a partial dissociation occurs with the formation of NiLX₂, L, NiL₂X⁺, and X^?. Using a spectrophotometric method stability constants K_2S of the complexes NiL₂X₂ are determined. A correlation exists between log K_2s and the pK- values of the quarternary ammonium ions derived from the ligands L. Sterical factors cause the exeptional position of the chelates of β-methylaminoethylpyridine-(2).     

Polymerisation von Methyl- und ?thylmethacrylaten mit Alkalimetall-Alkoxidderivaten des Poly?thylenoxids

Ohne Zusammenfassung     

Kinetik der Reaktion des Kobalt(II)-tetrasulfophthalocyanins mit Molekularsauerstoff

Ohne Zusammenfassung     

Zu einigen Besonderheiten des thermischen Zerfalls von Ni(II)-Komplexen mit dreizähnigen Schiffschen Basen

Zusammenfassung Es wurde eine Reihe von Komplexen des zweiwertigen Nickels mit den Schiffbasen H₂L,H₂L der Zusammensetzung NiL·ROH(R=Me, Et, Pr, i-Pr)und NiL ·ROH (R=Me, Et, Pr, i-Pr, Bu) hergestellt und deren thermischer Zerfall untersucht. Es wurde festgestellt, dass bei den Addukten NiL·ROH der Zerfall unter Abspaltung des Alkohols (Zwischenprodukt NiL) verläuft, während bei NiL·ROH sofort nach der Abspaltung des Alkohols zur Massenzunahme auf TG-Kurve durch Oxidation des Stoffes kommt. Das Plateau, das dem Zwischenprodukt NiL entspricht, ist hier nur in der Ineratmosphäre erhaltbar. Es wurden auch die Aktivierungsenergien für die Abspaltung des Alkohols berechnet.

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Ni(II) Schiff base complexes of compositions NiL ROH (R=Me, Et, Pr, i-Pr) and NiL·ROH (R=Me, Et, Pr, i-Pr, Bu) were prepared and investigated by methods of thermal analysis. The thermal decomposition of NiL·ROH led to NiL (plateau in TG curve), whereas NiL·ROH underwent a similar decomposition only in an inert atmosphere (N₂); thermal decomposition in air involved alcohol fragmentation, followed by a mass increase due to oxidation by atmospheric oxygen. The activation energy of alcohol fragmentation was calculated.

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NiL · ROH (R=-, -, - ) NiL-ROH (R=-, -, -, -, ). , NiL ] NiL — . , . .

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Wir möchten uns sehr herzlich bei Doz. RNDr. E. Jóna, CSc. und RNDr. I. Horváth, CSc. für die Messungen in der Stickstoffatmosphäre in SAV Bratislava bedanken.     

Zur Kenntnis von Dinitrito-kobalt(III)-Komplexen. II Kinetik der Isomerisierung und der Umsetzung von cis- und trans-Dinitrito-di(äthylendiamin)-kobalt(III)-perchloraten mit Stickstoffwasserstoffsäure

On Dinitrito Cobalt(III) Complexes. II. Kinetics of Isomerisation and Reaction of Cis and Trans Dinitrito Di(ethylenediamine) Cobalt(III) Perchlorates with Hydrazoic Acid After a reinvestigation of the kinetic data of the nitrito-nitro isomerisation of cis and trans dinitrito-di(ethylenediamine) cobaltic perchlorate, the kinetics of the reactions between both coordination compounds and hydrazoic acid, to yield the diaquo compounds, nitrogen and dinitrogen oxide, has been studied by gasvolumetric measurements in the temperature range from 1 to 15°C. In azide buffer solutions both reactions proceed independently of pH, in two stages bimolecular with regard to the complex ion and hydrazoicacid. In both cases the first stage velocity constant is five times greater than the second constant. The cis-compounds react approximately three times faster than the trans-compounds. Possible reasons for the observed facts are discussed.     

Untersuchung der Mangan(II)-carbonat-Thermolyse mittels Thermogravimetrie und Messung der spezifischen (BET)-Oberfläche

Zusammenfassung Mangan(II)-carbonat ist fast nie stöchiometrisch rein. Seine Zusammenzung kann richtiger mit einer allgemeinen Formel Mn(CO₃)_x(OH)_y · ·(H₂O)_z wiedergegeben werden. Die Indices dieser Formel und dadurch die Thermogramme und BET-Oberflächen ändern sich mit der Lagerungszeit, der Vorgeschichte, dem Fremdstoffgehalt usw. In Vakuum und Inertgasatmosphäre führt die thermische Zersetzung zu MnO. In Luftatmosphäre bildet sich zuerst, solange das entwickelte CO₂ seine Schutzgaswirkung ausübt, ebenfalls MnO, das aber sekundär, von Temperatur undP _O2 abhängig, rasch zu MnO₂, Mn₂O₃ und/oder Mn₃O₄ oxydiert wird. Die Kinetik der primären Zersetzungsreaktion und der sekundären Rückoxydationsreaktionen wird auf Grund der Thermogramme eingehend diskutiert. Die BET-Oberfläche, die, solange keine Zersetzung oder polymorphe Umwandlung stattfindet, mit steigender Temperatur im Sinne einer Clausius-Clapeyronschen Asymptote abnimmt, steigt während der Zersetzung des Carbonates, ein Maximum durchlaufend, stark an, und vermindert sich dann im Sinne der Asymptote der MnO-Sinterung nur, nachdem der CO₃-Index kleiner als 0,1 wird.

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Summary Manganese(II) carbonate is practically never stoichiometrically pure. Its formula can be more correctly represented by a general formula Mn(CO₃)_x(OH)_y·(H₂O)_z. The indices of this formula and hence the thermogram and BET-surface alter with the storage period, the previous history, the content of foreign materials, etc. The thermal decomposition leads to MnO in vacuo and an inert gas atmosphere. In the air, and as long as the CO₂ evolved exerts it protective action, MnO is likewise produced, but, secondarily and dependent on the temperature andP _O2 there is rapid oxidation to MnO₂, Mn₂O₃ and/or Mn₃O₄. The kinetics of the primary decomposition reaction and the secondary reoxidation reactions are discussed in detail on the basis of the thermogram. The BET-surface, which decreases asymptotically increases with rising temperature in the sense of a Clausius-Clapeyron asymptote so long as no decomposition or polymorphic transformation occurs, ascends greatly during the decomposition of the carbonate, passing through a maximum and then decreases in the sense of the asymptote of the MnO-sintering only, after the CO₃-index becomes less than 0.1.

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Résumé Le carbonate de manganèse-II n'est presque jamais stoechiométriquement pur. Sa composition peut être représentée d'une manière plus exacte par une formule générale Mn(CO₃)_x(OH)_y·(H₂O)_z. Les indices de cette formule, et par suite les thermogrammes et les surfaces BET, sont différents suivant le temps de stockage, les traitements préalables, la teneur en impuretés, etc. Dans le vide et en atmosphère inerte, la décomposition thermique conduit à MnO. En présence de l'air atmosphérique, il se forme d'abord également du MnO, tant que le gaz carbonique qui se dégage exerce son action de gaz protecteur. MnO s'oxyde ensuite, suivant la température etP _O2 rapidement en MnO₂, Mn₂O₃ et/ou Mn₃O₄. On discute en détail la cinétique de la réaction de décomposition primaire et celle des réactions secondaires d'oxydation en retour, d'après les thermogrammes. La surface BET qui se produit tant qu'il n'y a pas de décomposition ni de transformation polymorphe, diminue quand la température augmente, suivant une asymptote Clausius-Clapeyron, et augmente fortement lorsque la décomposition du carbonate passe par un maximum. Elle ne diminue ensuite suivant l'asymptote au frittage de MnO, qu'après que l'indice de CO₃ soit plus petit que 0,1.

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Vorgetragen bei einem gemeinsamen Seminar der Institute für physikalische bzw. anorganische und analytische Chemie der Universität Innsbruck, im Rahmen des Chemikertreffens des Vereins Österreichischer Chemiker, 1965.