Schiff-Basen aus 1,3-Dicarbonylverbindungen und Triaminen und ihre Fe (III)-, Co (III)-, Ni(II)- und Cu(II)-Komplexe

Schiff bases of 1,3-dicarbonyl compounds with triamines and their Fe(III), Co(III), Ni(II) and Cu(II) complexes The preparation of new hexadentate ligands obtained by the reaction of cis, cis-1,3,5-triaminocyclohexane (tach) or 1,1,1-tris (aminomethyl)ethane (tame) with an 2-ethoxymethylidene-1,3-dicarbonyl compound as well as their Fe(III), Co(III), Ni(II) and Cu(II) complexes is reported. Fe(III) and Co(III) yield neutral complexes with an octahedral N₃O₃-coordination sphere, Ni(II) and Cu(II) complexes with a square-planar coordination-sphere. In the later complexes one of the bidentate branches of the ligand is not deprotonated and stays uncoordinated.     

Kupfer(I)-Komplexe mit 1-Azadien-Chelatliganden und ihre Reaktion mit Sauerstoff

Copper(I) Complexes with 1-Azadiene Chelate Ligands and Their Reaction with Oxygen The reaction of the bidendate 1-azadiene ligands Me₂N? (CH₂)_n? N?CH? CH?CH? Ph with CuX results in the formation of the dimeric compounds [ A CuX]₂ and [ B CuX]₂ ( A : n = 2, B : n = 3, X: I, Cl). The structure of complex 1 [ A CuI]₂ was determined by X-ray crystal structure analysis. 1 consists of two tetrahedrally coordinated Cu atoms connected by two iodo bridges. (Cu? Cu bond length: 261 pm). The ligand Me? N(CH₂CH₂N?CH? CH?CH? Ph)₂ ( C ) reacts with CuX to form the monomeric complexes [ C CuX] ( 5 : X?I, 6 : X?Cl). The crystal structure of 5 shows that the ligand acts as a tridendate ligand. The bond lengths of the CuN(sp²) bonds are significantly shorter than the Cu? N(sp³) distance. Reacting the podand-type ligands N(CH₂CH₂? N?CH? R)₃ ( D : R?Ph, E : R?-CH?CH? Ph) with CuX yields the ionic complexes 7 [ D Cu][CuCl₂] and 8 [ E Cu][CuCl₂]. 7 was characterized by X-ray analysis which confirmed that D acts as a four-dendate podand ligand. The compounds 1 ? 8 are unreactive towards CO₂ but take up O₂ even at deep temperatures. At ?78°C the orange-red complex 4 [ B CuCl]₂ reacts with O₂ in CH₂Cl₂ to form a deep violet solution, but the primary product of the oxidation could not be isolated. It reacts at room temperature to form the green complex 9 [μ-Cl, μ-OH][ B CuCl]₂. The X-ray structure analysis of 9 confirms that a dimeric Cu^II complex is formed in which both a chloro- and a hydroxo group are bridging the monomeric units. The Cu^II centers exhibit a distorted tetragonal-pyramidal coordination. The pathway of the reaction with O₂ will be discussed.     

Kupfer(II)-Komplexe mit para- und diamagnetischen Semicarbazonliganden

A series of complexes formed between the copper(II) metal ion and the semicarbazone of the stable free radical 2-acetyl-2,5,5-trimethyl-4-phenyl-3-imidazoline-3-oxid-1-oxyl and the analogous hydroxylamine has been prepared. By analysis of the IR spectra of the complexes the coordination mode of the ligands was determined.

     

Herstellung und Eigenschaften einiger hydrocorphinoider Nickel(II)-Komplexe

Preparation and Properties of some Hydrocorphinoid Nickel(II)-Complexes Corphin derivatives synthesized earlier in our laboratory have been used for the preparation of tetrahydro- and hexahydrocorphinoid nickel(II)-complexes containing novel chromophore systems. The UV./VIS. and ¹H- and ¹³C-NMR. spectral data of these complexes were relevant to the structure determination of Factor F430 described in the following paper.     

Heterogene Reactionen fester Nickel(II)-Komplexe. XXI. Thermische Zersetzung und Stereochemie der Thiocyanato-Nickel(II)-Komplexe mit Pyridin-N-Oxid und Methylsubstituierten Pyridin-N-Oxiden

Heterogeneous Reactions of Solid Nickel(II) Complexes. XXI. Thermal Decomposition and Sterochemistry of Thiocyanato-Nickel(II) Complexes with Pyridine N-Oxide and Methylsubstituted Pyridine N-Oxides The thermal decomposition was studied for the complexes: Ni(NCS)₂(pyNO)₃ · H₂O (I), (pyNO = pyridine N-oxide), Ni(NCS)₂(2-MepyNO)₃ (II) Me = Methyl, Ni(NCS)₂(3-MepyNO)₂ · C₂H₅OH (III) and Ni(NCS)₂(4-MepyNO)₂ · H₂O (IV). On heating the solvent molecules bonded escape and then the decomposition of heterocyclic ligands sets in. The spectral and magnetic data indicate a pseudooctahedral configuration of the starting complexes as also of Ni(NCS)₂(pyNO)₃ (V), Ni(NCS)₂(3-MepyNO)₂ (VI) and Ni(NCS)₂(4-MepyNO)₂ (VII), i. e. of the initial complexes without the solvent molecules. For complexes of the type of [Ni(NCS)₂L₃] · xH₂O (L = pyNO, x = 0, 1; L = 2-MepyNO and x = 0) a dimeric structure is assumed, while for those of the type of [Ni(NCS)₂L₂] · xH₂O (C₂H₅OH) (L = 3-MepyNO and 4-MepyNO, x = 0 or 1) a polymeric structure is supposed.     

Neutrale und kationische Ruthenium(II)-Komplexe mit trifunktionellen Phosphanliganden

Neutral and Cationic Ruthenium(II) Complexes with Trifunctional Phosphane Ligands Compounds of the type [RuCl₂(RPX₂)₂] 4 – 7 (R = iPr, tBu; X = CH₂CH₂OMe, CH₂CO₂Me) were prepared by reacting RPX₂ with either RuCl₃ · 3H₂O or [RuCl₂(PPh₃)₃], respectively. In 4 – 7 the trifunctional phosphanes coordinate as bidentate ligands to the metal center through the phosphorus atom and the oxygen atom of a methoxy or carbonyl group. The lability of the Ru–O bond allows substitution reactions with CO, tert-butylisonitrile and phenylacetylene. The Ru–Cl bonds in 5 (R = tBu; X = CH₂CH₂OMe) can be cleaved upon treatment with one or two equiv of AgPF₆ yielding mono- or dicationic derivatives. In these complexes the ligands are coordinated to the metal center through the phosphorus and both of the oxygen donor atoms. The reaction of the phosphinoesterenolate compound 17 with Ph₂C=C=O leads to the insertion of two molecules of the ketene into the C–H bond of one of the five-membered metal-enolate rings to yield the “expanded” chelate complex 18 , the structure of which was determined by X-ray crystallography.     

Zur Revision Oxydationspotentiale der Orthophenanthrolin- und Dipyridyl-Eisen(II)-Komplexe

Ohne Zusammenfassung     

Cyanato-Kupfer(II)-Komplexe mit organischen Liganden. XV. Verschiedene Koordinationen und Kristallformen der Cyanato-Kupfer(II)-Komplexe mit Urotropin

Cyanato-Copper(II) Complexes with Organic Ligands. XV. Various Coordinations and Crystal Forms of Cyanato-Copper(II) Complexes with Urotropine Four forms of the compound Cu(NCO)₂(urt) · 2 H₂O (α, β, γ, δ) and two forms of the compound Cu(NCO)₂(urt) (α, β) (urt = urotropine) were prepared and studied by X-ray powder technique, as well as by other physical methods. The obtained results indicate that in all the compounds Cu(II) atoms are bridged by bidentate urotropine molecules and bonded always with two nitrogen atoms of NCO groups. The γ- and δ-ihydrate show a pseudotetrahedral configuration, other compounds are five- or sixcoordinate owing to bridging function of NCO groups. Water in the dihydrates is hydrogen bonded in the crystal structure. The crystal structures of α- and β- like γ-and δ-ihydrates are very similar; the last two may be regarded as distortion isomers.     

Darstellung und Eigenschaften löslicher und Polysiloxangebundener (Ether-Phosphan)ruthenium(II)-Komplexe

Preparation and Properties of Soluble and Polysiloxane-Supported (Ether-Phosphine)ruthenium(II) Complexes Phosphine-modified Polysiloxanes of the type x SiO₂ · [SiO_3/2(CH₂)₆P(Ph)R] (x = 0 – 3, I–IV ) were prepared by hydrolytic condensation of (MeO)₃Si(CH₂)₆P(Ph)R [ 1 ; R = CH₂CH₂OMe ( a ), CH₂C₄H₇O ( b ), CH₂C₄H₇O₂ ( c ), Ph ( d )]. Crosslinking was achieved by cocondensation of 1 and Si(OEt)₄. 2 SiO₂ · [SiO_3/2(CH₂)₆P(Ph)CH₂CH₂OMe] ( IIIa ) was investigated by means of ³¹P and ²⁹Si CP-MAS-NMR-spectroscopy, especially in view of a quantification of silyl species which revealed the following ratios: T₂:T₄:Q₂:Q₃:Q₄ = 76:158:48:135:82. Reaction of RuCl₂(PPh₃)₃ with 3 moles of 1a gave fluxional RuCl₂(P∩O)(P～O)₂ ( 4a ). From its temperature dependent ³¹P{¹H}-NMR spectrum the temperatures of coalescence and the corresponding activation enthalpies could be estimated at -25°C (46 kJ · mol^?1) and +20°C (55 kJ · mol^?1). Soluble 1a-d as well as their insoluble counterparts I-IV were treated with [RuCl₂(CO)₂]_n to give all-trans-RuCl₂(CO)₂(PR₃)₂ ( 6 ). On heating (120°C) 6 could be transformed into isomeric cis, cis, trans-RuCl₂(CO)₂(PR₃)₂ ( 7 ). Decarbonylation occurred on irradiation of 6 . Polysiloxane-supported ruthenium complexes were proved to be active in the heterogeneous hydrogenation of crotonaldehyde. Thus, at p(H₂) = 50 bat, T = 120°C, reaction time = 190 min, and at a molar ratio of aldehyde: Ru = 250:1, all-trans-RuCl₂(CO)₂(P～O)₂ ( 6f , O,P = IIIa ) effected a conversion of 50%, crotyl alcohol being formed in comparatively high selectivities. Moreover, no loss of metal or ligand from the support could be observed.     

Über Reaktionen Oxygenierter Kobalt (II)-Komplexe. X. 1,4,7,10-Tetraazadecan-kobalt (II) und 4, 7-dimethyl-1,4,7,10-tetraazadecan-kobalt (II) als sauerstoffträger

Reactions of oxygenated cobalt (II) complexes. X. 1,4,7,10-tetraazadecanecobalt (II) and 4,7-dimethyl-1,4,7,10-tetraazadecanecobalt (II) as dioxygen carriers

1 IX: siehe [1].

Oxygenation of cobalt (II) chelates with fourdentate amines such as 1,4,7,10-tetraazadecane (= tad) in aqueous solution yields μ-peroxo-μ-hydroxo-dicobalt (III) complexes. Due to facultative ligand disposition of the amine, 8 different diastereoisomers are possible. Introducing methyl groups in positions 4 and 7 of tad destabilizes the isomers with β-configuration. A crystallized perchlorate, obtained by oxygenation of 4, 7-dimethyl-1,4,7,10-tetraazadecanecobalt (II) (= dmtad) in alcaline solution, proved to be of the expected μ-peroxo-μ-hydroxo type. The ligand configuration is and lattice constants a (ΔΔ/ΛΛ). The X-ray structure was solved by Patterson's method and refined to R = 0.093. The crystals are orthorhombic with space group Pna2₁ and lattice constants a = 14.632 (4), b = 17.525 (5), c = 12.888 (5) Å. In its UV./VIS. absorption spectrum and its solution reactivity the binuclear cation is closely related to oxygenation products obtained with the chelate of unsubstituted tad. The kinetic parameters of the decomposition reaction of the μ-peroxo complexes in acidic solution are compared. The binuclear cations with 4, 7-dimethyl-1,4,7,10-tetraazadecane as ligand are generally more reactive. In slightly alcaline solution isomerization of the μ-peroxo-μ-hydroxo complexes has been observed.     

Nickel(II)- und Kobalt(II)-Komplexe des trans-2-Äthylmercapto-cyclohexyl-phenylphosphins

Preparation and properties of nickel(II) and cobalt(II) chelates of the bidentate ligand trans-2-ethylthio-cyclohexyl-phenylphosphine (ÄMCPP) are described. Three types of nickel(II) complexes have been obtained from ÄMCPP: the four-coordinated, square planar [Ni(ÄMCPP)₂]X₂ (X = J, Br, ClO₄); five-coordinated [Ni(ÄMCPP)₂X]X (X = Cl, NCS), [Ni(ÄMCPP)₂X]BPh₄ (X = Cl, NCS) and the octahedral [Ni(ÄMCPP)₂Cl₂]. Cobalt(II) forms tetrahedral 1.1-[Co(ÄMCPP)X₂] (X = Br, Cl) and 1.2-Co(ÄMCPP)₂X₂(X = Br, Cl, NCS) complexes. All compounds were characterized by electronic reflectance and absorption spectra, conductivity and magnetic measurements.     

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.