Zinn(IV)-Komplexe mit dreizähnigen diaciden Liganden

Tin(IV) Complexes with Tridentate Diacidic Ligands By template reactions including bis(acetylacetonato)-dichloro-tin(IV) and O-aminophenol as well as o-aminothiophenol, benzoylhydrazine, and thiobenzoylhydrazine the tin chelates of tridentate diacidic ligands containing ligator atoms were prepared. To characterize the compound, IR, UV-VIS and Mössbauer spectroscopy were used. Crystal structure analyses demonstrate the existence of disturbed octahedral structures. Bis[acetylacetonbenzoylhydrazonato(2-)]tin(IV): space group P2₁/c, Z = 4, 2501 observed unique reflections, R = 0.045. Lattice dimensions at 20°C: a = 992.3, b = 2405.5, c = 1071.8pm, β = 116.94°. Bis[acetylacetonthiobenzoylhydrazonato(2-)] tin(IV): space group P2₁/c, Z = 4, 3603 observed unique reflections, R= 0.029. Lattice dimensions at 20°C: a = 1581.5, b = 947.8, c = 1644.9pm, β = 90.32°.     

Oxofreie Vanadium(IV)-Komplexe mit dreizähnigen diaciden Liganden. Struktur von Bis[2,2′-dihydroxy-azobenzenato(2−)]vanadium(IV)

Non-oxo Vanadium(IV) Complexes with Tridentate Diacidic Ligands. Molecular Structure of Bis[2.2′-dihydroxy-azobenzenato(2?)]vanadium(IV) By the reaction of tris(acetylacetonato)vanadium(III) with tridentate diacidic ligands non-oxo vanadium(IV) complexes of these ligands were synthesized. The complexes were characterized by mass spectrometry. Electrochemical studies show that the complexes are reversibly oxidized or reduced. Bis[2,2′-dihydroxy-azobenzenato(2?)]vanadium(IV) has a distorted trigonal-prismatic structure. Crystallographic data see ?Inhaltsübersicht”?.     

Mangan(IV)-Komplexe mit dreizähnigen diaciden Liganden. Kristallstruktur von Acetylacetonato-salicylaldehydbenzoylhydrazonato(2−)-methanol-mangan(III)

Manganese(IV) Complexes with Tridentate Diacidic Ligands. Crystal Structure of Acetyl-acetonato-salicylaldehydebenzoylhydrazonato(2?)-methanol-manganese(III) The manganese(IV) chelates of salicylaldehyde benzoylhydrazone and salicylaldehyde salicylhydrazone were synthesized by ligand exchange reactions using bis(acetylacetonato)manganese(II), tris(acetylacetonato)manganese(III) as well as manganese(III) acetate. The brown complexes show the expected molecular ions in the APCI mass spectra. As an intermediate compound acetyacetonato-salicylaldehydebenzoylhydrazonato(2?)-methanol-manganese(III) was isolated and characterized by X-ray structural analysis. Crystallographic data see “Inhaltsübersicht”.     

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.     

Titan(IV)-Komplexe mit dreizähnigen diaciden Liganden. Kristallstruktur von Bis[2,6-diphenacylpyridinato(2 –)]titan(IV)

Titanium(IV) Complexes with Tridentate Diacidic Ligands. Crystal Structure of Bis[2,6-diphenacylpyridinato(2–)]titanium(IV) The titanium(IV) chelates with 2,2′-dihydroxy-azobenzene, salicylaldehyde-2-hydroxyanil, 2-(2′-hydroxyphenyl)-8-quinolinol, 2,6-diphenacylpyridine as well as with aroylhydrazones of salicylaldehyde, benzoylacetone and thenoyltrifluoroacetone were synthesized by ligand exchange reactions of titanium(IV)-isopropoxide. The compounds are red or black in colour and were identified by distinct molecular peaks in the mass spectra. The crystal and molecular structure was determined for bis[2,6-diphenacylpyridinato(2–)] titanium(IV). Crystallographic data see “Inhaltsübersicht”.     

Komplexbildung und Extraktion von Molybdän(VI) mit zweizähnigen Liganden

Coordination and Extraction of Molybdenum(VI) with Bidentate Ligands A series of bidentate ligands as well as their thio derivatives from the groups of 8-quinolinols, β-diketones, acylpyrazolones, and N-acyl-phenylhydroxylamines was studied for the ability to extract molybdenum(VI) from heptamolybdate. The extraction principally runs only in acidic medium, sulfur-containing extractants having no advantage. The composition of the complexes was determined by the isolation of compounds in the solid state and also by the interpretation of distribution data.     

Strukturuntersuchungen an Derivaten des Nickelkomplexes Ni(ONO) (ONO2− = Dianion einer dreizähnigen Schiffschen Base)

Structure Studies on Derivatives of the Nickel Complex Ni(ONO) (ONO^2? = Dianion of a Tridentate Schiff Base) The thermodynamically stable form of the solvent free, formally tri-coordinate complex Ni(ONO) (ONO^2? = dianion of N-(2-hydroxyphenyl)-2-ethoxycarbonyl-3-ox(o-butene(1) amine(1)) as well as the mono adducts Ni(ONO)X with X = ammonia and X = diphenyl thiourea (DPT) have been characterized by X-ray structure analysis. In all cases the central atom is coordinated in a square-planar fashion, only for the adduct Ni(ONO)(DPT) a pyramidal distortion is observed which is due to the formation of hydrogen bonds. The solvent free form is a dimer [Ni(ONO)]₂, and represents one of the few examples of dinuclear nickel complexes with a planar [NO₃] coordination. The phenolic O-atoms act as bridging ligands. Due to their reduced π-donor strength the bond lengths Ni? O trans to the bridges are significantly shortened. In contrast to the analogous complex with an aliphatic bridge, “NiEIA”, both halves of the dimeric molecules are coplanar with a Ni? Ni distance of 3.29 Å.     

Komplexchemie Polyfunktioneller Liganden. XXXIII. IR-, FIR- und RAMAN-Spektroskopische Untersuchungen an Metalltricarbonylderivaten mit vierzähnigen P- und As-Liganden im Bereich 2000–150 cm−1

Complex Chemistry of Polyfunctional Ligands. XXXIII. IR, FIR and Raman-Spectroscopic Studies on Metaltricarbonyl Derivatives of Tetradendate P- and As-Ligands in the Region 2000–150 cm^?1 The IR- (2000–250 cm^?1), FIR- (350–150cm^?1) and RAMAN -spectra (2000–150 cm^?1) of the tetradendate ligands C[CH₂E(C₆H₅)₂]₄ (E = P, As) and of the complexes of the type cis-M(CO)₃(R₂ECH₂)₃C(CH₂ER₂) (M = Cr, Mo, W; E = P, As; R = C₆H₅) have been obtained. A comparison of the spectra of these compounds and consideration of previously reported data of analogous compounds allowed the assignment of all ligand vibrations. After localisation of the ligand vibrations an assignment of the v (CO) (A₁ + E), δ (MCO) (A₁ + 2E, v (MC) (A₁ + E) and v (ME) (A₁) modes was possible for the coordination polyhedra cis-M(CO)₃)E₃ (point group C_3v). The v(ME) (E) modes were unobserved by its very low frequency.     

ZrIV‐ und TaV‐Komplexe mit methanoverbrückten Bis(aryloxy)‐Liganden

Zr^IV and Ta^V Complexes with Methano‐Bridged Bis(aryloxy) Ligands The bis(aryloxy) ligand precursor compounds bis(2‐trimethylsiloxy‐5‐tbutylphenyl)methane (L–SiMe₃) and its bromoderivative (2‐trimethylsiloxy‐3‐bromo‐5‐tbutylphenyl)(2′‐trimethylsiloxy‐5′‐tbutylphenyl)methane (L^Br–SiMe₃) are prepared in analogy to the corresponding calixarenes in excellent yields. X‐ray structure analysis for L^Br–SiMe₃: space group P2₁/c, a = 12.462(7), b = 10.466(6), c = 23.315(14) Å, β = 105.02(4)°, V = 2937(3) ų, Z = 4. L–SiMe₃ and L^Br–SiMe₃ react with Zr^IV and Ta^V chlorides in very good yields forming di‐ and trinuclear complexes. From the reaction of CpZrCl₃ with L^Br–SiMe₃ in the ratio of 3 : 2 a Zr₃ complex ( 7 ) is obtained, with one L^Br ligand only, which Zr atoms are bridged by a μ₃‐oxygen. The X‐ray structure analysis of 7 (space group R 3, a = 33.23(6), c = 24.47(8) Å, V = 23405(128) ų, Z = 18) additionally reveals that one phenolato oxygen atom of the L^Br ligand is terminally bound to a distorted tetragonal‐pyramidal coordinated Zr atom, while the second phenolato oxygen atom of the L^Br ligand forms a bridge to another Zr atom with a distorted octahedral coordination. The third Zr atom is also found in a distorted octahedral coordination mode. The reactions of L–SiMe₃ and L^Br–SiMe₃ with CpTaCl₄ and TaCl₅ yield dinuclear Ta complexes with a bridging bis(aryloxy) ligand. NMR spectroscopic data point out that the coordination of the bis(aryloxy) ligands in the Ta complexes very much resembles that in the Zr₃‐complex with one terminal and one bridging phenolato oxygen atom. The Zr₃ and the Ta complexes L^BrTa₂Cp₂Cl₆ and LTa₂Cl₈ were tested with respect to their catalytic properties in olefin polymerisation reactions in the presence of MAO.     

Vanadium-Komplexe mit dreizähnigen diaciden Liganden. Die Kristallstrukturen von Bis[acetylacetonthiobenzoylhydrazonato(2-)]vanadium(IV), Methoxo-oxo-[salicylaldehydthiobenzoylhydrazonato(2-)]vanadium(V) und Methoxo-oxo-[salicylaldehydbenzoylhydrazonato(2-)]methanolvanadium(V)

Vanadium Complexes with Tridentate Diacidic Ligands. The Crystal Structures of Bis[acetylacetonato-thiobenzoylhydrazonato(2-)]vanadium(IV), Methoxo-oxo-[salicylaldehyd-thiobenzoylhydrazonato(2-)]vanadium(V), and Methoxo-oxo-[salicylaldehydbenzoylhydrazonato(2-)]methanol Vanadium(V) By template reactions of bis(acetylacetonato)oxovanadium(IV) and bis(salicylaldehydato)oxo-vanadium(IV), respectively, with benzoylhydrazine, thiobenzoylhydrazine, and 2-aminophenol the vanadium(IV) complexes V(LLL)₂ of tridentate azomethine ligands LLL were synthesized. The complexes were characterized by EPR spectroscopy and by absorption spectroscopy. From the complex V(LLL)₂ ( 1 ), in which LLL is acetyl-aceton-thiobenzoydrazonate(2-), the crystal structure analysis was solved. The vanadium atom in 1 is coordinated trigonal-prismatically by two N, 0 and S atoms. Furthermore, the 0x0 vanadium(V) complexes[VO(LLL)(OCH,)] (6) with LLL = salicylaldehyd-thio-benzoylhydrazonato(2-) and [VO(LLL)(OCH₃)· -CH₃OH] (7) with LLL = salicylaldehydbenzoylhydrazonato(2-) were identified by X-ray diffraction and by IR spectroscopy in the reaction products. Crystallographic data for 1, 6 , and 7 see ?Inhaltsübersicht”?.     

Nickel(I)‐Komplexe mit 1,1′‐Bis(phosphino)ferrocenen als Liganden

Nickel(I) Complexes with 1,1′‐Bis(phosphino)ferrocenes as Ligands The thermically stable monomeric Nickel(I) complexes [(d^tbpf)Ni(acac)] ( 1 ) and [(dⁱppf)NiCl] ( 2 ) were synthesized and characterized by elemental analyses, EPR spectroscopy, and by X‐ray crystal structure analyses of single crystals (d^tbpf: 1,1′‐bis(di‐tertbutylphosphino)ferrocene; dⁱppf: 1,1′‐bis(diisopropylphosphino)ferrocene). 1 is formed by reduction of Ni(acac)₂ with triethylaluminium in the presence of d^tbpf, together with the nickel(0) complex [(d^tbpf)Ni(C₂H₄)]. 1 contains a Ni^I atom surrounded of two O‐ and two P donor atoms in a distorted tetrahedral coordination. 2 was obtained by reduction of [(dⁱppf)NiCl₂] with NaBH₄. In 2 the nickel(I) atom adopts trigonal planar coordination.     

Metallcarbonylkomplexe mit mehrzähnigen ringförmigen Liganden. I. Pentacarbonylkomplexe des s-Trithians und verwandter Verbindungen

Carbonyl Metal Compounds with Polydentate Cyclic Ligands. I. Pentacarbonyl Complexes of s-Trithiane and Related Compounds The complexes (RCHS)_nM(CO)₅ (R = H, CH₃, n = 3; R = H, n = 4; M = Cr^, Mo, W) were prepared from the tetrahydrofuran pentacarbonyl metal compounds and the respective ligands. The Cotton-Kraihanzel force constants of these complexes indicate the sulfur ligands to be slightly more basic than triphenylphosphine. The trimethyltrithiane complexes (R = CH₃, n = 3) exhibit rapid intramolecular exchange of the M(CO)₅-group along the three coordination centers of the ligand.