Komplexe des Kobalt(II)-Malonats mit organischen Basen (Pyridin und Urotropin)

Ohne Zusammenfassung     

Komplexe von Cu(II), Zn(II), Ni(II) und Mn(II) mit N-m-Tolyl-p-methylbenzhydroxamsäure

The thermodynamic proton ligand and metal ligand stability constants of N-m-tolyl-p-methylbenzohydroxamic acid with Cu(II), Zn(II), Ni(II), and Mn(II) have been determined at 25° and 35° in several dioxane-water media. The pK _a and logK ₁ (logK ₂ or log ₂) varies linearly with the mole fraction of dioxane at a given temperature but not linearly with the reciprocal of dielectric constants of the medium. Values of G ^o, H ^o, and S ^o are tubulated. The stabilities of the complexes mostly follow the order of electron affinities of the metal ions. An attempt has been made to calculate the ligand field stabilization energy of the complexes.

---

---

Mit 2 Abbildungen     

Doppelkomplexsalze von Co(II), Ni(II) und Cu(II) mit Thioharnstoffliganden im Kationkomplex und Thiocyanatliganden im anionkomplex

Three new double complex compounds of the following type were obtained: [CoThio ₄][Co(SCN)₄], [NiThio ₄][Ni(SCN)₄] and (CuThio ₄) (CuCo(SCN)₄). The melting points of the compounds were determined, and the molecular weight of the first. The IR-spectra were studied and the metal-ligand bond interpreted. It was shown that the metal-thiourea bond in all compounds is formed via the sulphur atom. In the complex anion of the first and second compounds Co(II) and Ni(II) are coordinated with SCN^– through the nitrogen atom. In the third, more complicated compound, Cu(II) is coordinated to SCN^– through the sulphur atom, and Co(II) through the nitrogen atom, a bridging bond being formed.     

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.     

Komplexe der Ionen Ni2+ und Co2+ mit Sulfiden (Seleniden) di-, tri- und tetratertiärer Arsane

Complexes of the Ni²⁺ and Co²⁺ Ions with Sulfides and Selenides of di-, tri-, and tetratertiary Arsanes The reaction of the sulfides (selenides) of di-, tri- and tetra-tertiary arsanes with the salts CoCl₂ · 6 H₂O respectively Ni(ClO₄)₂ · 6 H₂O results in the formation of chelat complexes, in which the metal ions are tetrahedrally surrounded by the ligands. The UV spectra of the complexes are discussed.     

Neue Komplexe des Titans mit silylierten Aminoiminophosphoran- und Sulfodiimidliganden

New Complexes of Titanium with Silylated Aminoiminophosphorane and Sulfodiimide Ligands TiCl₄ forms a 1 : 1 adduct with S(NSiMe₃)₂ to give compound 1 and with Me₂S(NSiMe₃)₂ compound 2 , respectively. The reaction of TiCl₄ with Ph₂S(NSiMe₃)₂ yields the disubstituted compound Ph₂S(NTiCl₃)₂X₄THF 3 which crystallizes in space group P1 . Reaction of TiCl₄ with (Me₃Si)₂NPPh₂NPPh₂NSiMe₃ leads to an exchange of one silyl group with a TiCl₃ moiety. In this molecule the Ti-atom is only four-coordinated. The compound crystallizes in the space group P2₁/c. No chelate complexes are formed by reactions of CpTiCl₃, Cp*TiCl₃ and Cp*TiF₃ with Ph₂P(NSiMe₃)₂H, this is shown by X-ray structural analysis of Cp*TiCl₂NPPh₂NHSiMe₃ 6 . Crystals of 6 are obtained in space group P1 .     

Phosphanimin‐Komplexe des Berylliums und Phosphaniminato‐Komplexe mit Heterokubanstruktur

Phosphaneimine Complexes of Beryllium and Phosphoraneiminato Complexes with Heterocubane Structure Beryllium dichloride reacts with the silylated phosphaneimine Me₃SiNPEt₃ in dichloromethane solution to give the monomeric donor‐acceptor complex [BeCl₂(Me₃SiNPEt₃)] ( 1 ). Under cleavage of trimethylchlorosilane the thermolysis of 1 at 160 °C leads to the formation of the phosphoraneiminato complex [BeCl(μ₃‐NPEt₃)]₄ ( 2 ) with heterocubane structure. In the presence of BeCl₂ 1 reacts in the melt to give the phosphoraneiminato complex [Be₄Cl₄(μ₃‐Cl)(μ₃‐NPEt₃)₃] ( 3 ), the structure of which corresponds with the structure of 2 by substitution of a ligand (μ₃‐NPEt₃)^— by a μ₃‐chloro ligand. As a by‐product from the synthesis of 2 in dichloromethane solution the phosphaneimine complex [BeCl₂(μ‐HNPEt₃)]₂·CH₂Cl₂ ( 4 ·CH₂Cl₂) can be obtained. Its dimeric units form dimers [{BeCl₂(μ‐HNPEt₃)}₂]₂ with symmetry D₂ via Cl···H‐N hydrogen bridges. The compounds 1 — 4 ·CH₂Cl₂ are characterized by X‐ray structure determinations, 1 — 3 additionally by IR spectroscopy. 1 : Space group C2/c, Z = 8, lattice dimensions at 193 K: a = 1502.5(1), b = 801.8(1), c = 2609.6(2) pm, β = 96.15(1)°, R₁ = 0.0523. 2 : Space group C2/c, Z = 4, lattice dimensions at 193 K: a = 1992.2(2), b = 1054.8(1), c = 1950.6(2) pm, β = 114.82(1)°, R₁ = 0.0275. 3 : Space group P2₁2₁2₁, Z = 4, lattice dimensions at 193 K: a = 1159.5(1), b = 1199.0(1), c = 2251.1(2) pm, R₁ = 0.0399. 4 ·CH₂Cl₂: Space group Ccca, Z = 8, lattice dimensions at 193 K: a = 1454.6(1), b = 2795.7(3), c = 1235.6(1) pm, R₁ = 0.0349.     

Die Chelate von Co(II), Ni(II), Cu(II), Zn(II) und Cd(II) mit Malonsäurehydrazid und dessen Arylidenderivaten

The metal chelates formed by the reaction of Co²⁺, Cu²⁺, Ni²⁺, Zn²⁺, and Cd²⁺ with malonic hydrazide and its arylidene derivatives are investigated. The i.r.-absorption spectra of the solid compounds supported the tetradentate character of these compounds; they also show that the ligand still attained the keto form. The shift of the C=O, C=N bands is utilized in determining the coordination bond length. The stoichiometry of the metal complexes, as studied by spectrophotometric and conductometric methods, is found to be metal ion: ligand =11. The apparent formation constants of the malonic hydrazide complexes are also determined.

---

---

Mit 4 Abbildungen     

Neue Komplexe des Titans mit Bis(trimethylsilyl)amido-Liganden

New Complexes of Titanium with Bis(trimethylsilyl)amido Ligands The reaction of cp′TiCl₃ with LiN(SiMe₃)₂ · Et₂O 1 yield the compounds cp′TiCl₂N(SiMe₃)₂ (cp′ = C₅H₅ 2 , C₅H₄SiMe₃ 3 , C₅H₃(SiMe₃)₂ 4 , C₅Me₅ 5 ) and cp′TiCl[N(SiMe₃)₂]₂ (cp′ = C₅H₅ 6 ). Compound 2 was characterized by an X-ray structural analysis with space group P2₁/n and unit cell dimensions of a = 1 660.9(7), b = 688.6(3), c = 1 739.1(8) pm and β = 117.18(3)°.     

Untersuchungen über Bildung von Komplexen von Arylaminoanthrachinonen mit zweiwertigen Ionen von Übergangsmetallen, 1. Mitt.: Komplexe von Alizarin-cyaningrün und Alizarin-reinblau B mit Fe(II), Mn(II), Co(II), Ni(II) und Cu(II)

The complexes of 1,4-di(4-methylanilino)-anthraquinone (alizarin cyanin green) and 1-amino-2-bromo-4(2-sulpho-4-methylanilino)anthraquinone (alizarin pure blue B) with Fe(II), Mn(II), Co(II), Ni(II) and Cu(II) have been investigated and characterized on the basis of elemental analysis, conductometric, electronic and infrared spectral studies. The values of logB ^* for the different complexes are determined. I. R. spectra of the ligands in the solid chelates indicate that the bonding sites in the chelates are the -imino-nitrogen and the oxygen of its neighbouring C=O group. The chelate formation leads to proton displacement.     

Komplexe von Cu(II) und NI(II) mit Oxalamid-N,N′-diessigsäure

Ohne Zusammenfassung     

Komplexe aus Kupfer(II) und Acetylaceton

The complex formation between copper(II) and acetylacetonate (L)^* has been studied by potentiometry and distribution between CHCl₃ and water. The experimental data are interpreted by postulating the following equilibria: $$\begin{gathered} Cu^{2 + } + L \rightleftharpoons CuL1g \beta _1 = 8.42 \pm 0.10 \hfill \\ Cu^{2 + } + 2 L \rightleftharpoons CuL_2 1g \beta _2 = 15.47 \pm 0.10 \hfill \\ \left( {CuL_2 } \right)_{aq} \rightleftharpoons \left( {CuL_2 } \right)_0 1g \lambda _B = 1.80 \pm 0.10 \hfill \\ \end{gathered} $$ In order to study the complex formation, the protonation constant (k) of acetylacetonate and the distribution coefficient λ _A of acetylacetone in the same experimental conditions were required. It was found: lgk=9.05±0.03; λ _A = 1.20 ± 0.02.     

Komplexe des Nickels mit p-Methylbenzamidoxim

Zusammenfassung Die Komplexbildung des p-Methylbenzamidoxims (pMB) mit Ni²⁺ wurde in neutraler und alkalischer Lösung spektrophotometrisch untersucht. In neutraler Lösung wird ein grüner Komplex 11 gebildet, dessen Bildungskonstante ₁=1,12 ist. In alkalischer Lösung werden zwei Komplexe (11 und 12) gebildet mit Bildungskonstanten ₁=4·10⁵ und ₂=0,2.

---

Nickel complexes with p-methyl benzamide oxime

The complex formation of p-methyl benzamidoxime with Ni²⁺ was studied spectrophotometrically in neutral and in alkaline solution. A green complex 11 is formed in neutral solution. Its formation constant is ₁=1.12. In alkaline solution two complexes (11 and 12) are formed. Their formation constants are ₁=4·10⁵ and ₂=0,2 resp.

---

---

Mit 6 Abbildungen     

Komplexe des Kobalts mit o-Methylbenzamidoxim

Zusammenfassung Die stufenweise Komplexbildung des Co²⁺ mit o-Methylbenzamidoxim (oMB) gibt in alkalischer Lösung zwei Komplexe, deren Zusammensetzung 11 und 12 ist. Die Bildungskonstanten wurden nach graphisch-logarithmischen Methoden bestimmt. Die Bildungskonstanten sind ₁=(4,1±0,6)·10⁴ und ₂ = 0,41 bei 25° C und Ionenstärke =1.

---

Co(II) complexes of o-methylbenzamidoxime

In alkaline solution 11 and 12 complexes are formed stepwise from Co²⁺ and o-methylbenzamidoxime. The ligand numbers and the formation constants were determined from spectrophotometric data by logarithmic graphical methods. The formation constants are ₁=(4,1±0,6)·10⁴ and ₂ = 0,41 at 25° C and =1.

---

---

Mit 3 Abbildungen     

Komplexe des Blei(IV) mit zweizähnigenSchiffschen Basen

Zusammenfassung Es wurden Komplexe des Blei(IV)chlorids mit zweizähnigenSchiffschen Basen hergestellt. Aus den Analysenergebnissen ergibt sich die Stöchiometrie als 12. Die Komplexe sind inDMF Nichtelektrolyte und scheinen oktaedrische Struktur zu besitzen. Die UV- und IR-Spektren der Komplexe werden diskutiert und mögliche Strukturen vorgeschlagen.

---

Complexes of lead(IV) with bidentate schiff bases

Complexes of lead(IV) chloride with bidentateSchiff bases have been prepared. The analytical data indicate 12 stoichiometry. The complexes are nonelectrolytes inDMF, and appear to be octahedral. The UV and infrared spectra of the complexes are discussed and possible structures have been proposed.

---

---

Mit 2 Abbildungen     

Bromokomplexe von Co(II) und Ni(II) in Acetonitril,Propandiol-1,2-carbonat und Trimethylphosphat

Zusammenfassung Die Bildung von Bromokomplexen von Co(II) und Ni(II) wird in Acetonitril (AN), Propandiol-1,2-carbonat (PDC) und Trimethylphosphat (TMP) auf spektrophotometrischem, potentiometrischem und konduktometrischem Wege untersucht. Folgende Koordinationsformen dürften vorliegen: [CoBr]⁺ (oktaedrisch inAN undTMP), CoBr₂ (tetraedrisch inAN, oktaedrisch inTMP), [CoBr₃]^– (tetraedrisch inAN, oktaedrisch inTMP), [CoBr₄]^2– (tetraedrisch inAN undPDC, oktaedrisch inTMP), [NiBr]⁺ (oktaedrisch inAN), NiBr₂ (tetraedrisch inAN, oktaedrisch inTMP), [NiBr₃]^– (tetraedrisch inAN), [NiBr₄]^2– (tetraedrisch inAN undPDC, oktaedrisch inTMP).

---

The formation of bromo complexes of Co(II) and Ni(II) is investigated in acetonitrile (AN), propanediol-1,2-carbonate (PDC) and trimethylphosphate (TMP) by spectrophotometric, potentiometric and conductometric methods. The following coordination forms are reported: [CoBr]⁺ (octahedral inAN andTMP), CoBr₂ (tetrahedral inAN, octahedral inTMP), [CoBr₃]^– tetrahedral inAN, octahedral inTMP), [CoBr₄]^2– (tetrahedral inAN andPDC, octahedral inTMP), [NiBr]⁺ (octahedral inAN), NiBr₂ (tetrahedral inAN, octahedral inTMP), [NiBr₃]^– (tetrahedral inAN), [NiBr₄]^2– (tetrahedral inAN andPDC, octahedral inTMP).

---

---

Mit 8 Abbildungen     

Komplexe zwischen Eisen(II)- und Tartrat-Ion

The formation of complexes between iron(II) and tartrate ion (L) has been studied at 25° C in 1m-NaClO₄, by using a glass electrode. The e.m.f. data are explained with the following equilibria: $$\begin{gathered} Fe^{2 + } + L \rightleftarrows FeL log \beta _1 = 1,43 \pm 0,05 \hfill \\ Fe^{2 + } + 2L \rightleftarrows FeL_2 log \beta _2 = 2,50 \pm 0,05 \hfill \\\end{gathered} $$ The protonation constants of the tartaric acid have been determinated: $$\begin{gathered} H^ + + L \rightleftarrows HL logk_1 = 3,84 \pm 0,03 \hfill \\ 2H^ + + L \rightleftarrows H_2 L logk_2 = 6,43 \pm 0,02 \hfill \\\end{gathered}$$ .     

Komplexe aus Cadmium(II)- und Oxalat-ion

Complex formation between Cd(II) and oxalate has been studied before the precipitation at 25°C and 1M-NaClO₄, by means of glass- and cadmium amalgam electrodes. The e.m.f. data are explained with the following equilibrium: $$Cd^{2 + } + C_2 O_4^{2 - } \rightleftharpoons CdC_2 O_4 \log {\text{ }}\beta _1 = 2.75 \pm 0.05$$