Die Reaktion von TiCl4 und ZrCl4 mit (SeCN)2

Reaction of TiCl₄ and ZrCl₄ with (SeCN)₂ By reaction of TiCl₄ and ZrCl₄ with (SeCN)₂ in CS₂ the compounds TiCl₃NCSe and ZrCl₃NCSe were obtained. According to their vibrational spectra, the selenocyanate groups form bridges between the metal atoms via their N and Se atoms.     

Silanolato-Komplexe von Titan und Zirconium. Die Kristallstrukturen von Cp2TiCl(OSiPh3) und Cp2ZrCl(OSiPh3)

Silanolato Complexes of Titanium and Zirconium. The Crystal Structures of Cp₂TiCl(OSiPh₃) and Cp₂ZrCl(OSiPh₃) The title compounds have been prepared by the reaction of Cp₂MCl₂ (M = Ti, Zr) with triphenylsilanole in diethylether in the presence of piperidine. They form only sparingly moisture sensitive orange (Ti) or colourless (Zr) crystal needles, which were characterized by X-ray crystallography. Cp₂TiCl(OSiPh₃): Space group P2₁/n, Z = 4, structure solution with 3961 observed unique reflections, R = 0.057. Lattice dimensions at 20°C: a = 1029.6, b = 1719.3, c = 1388.9 pm, β = 100.69°. The compound forms monomeric molecules with bond lengths TiO of 184.2 pm, SiO of 161.5 pm, and a TiOSi bonding angle of 164.5°. Cp₂ZrCl(OSiPh₃): Space group P3 , Z = 18, structure solution with 2799 observed unique reflections, R = 0.047. Lattice dimensions at ?20°C: a = b = 3518, c = 1058.3 pm. The structure consists of three symmetry-independent monomeric molecules, which differ only slightly. The bond lengths are (in average): ZrO 196.4 pm, SiO 162.1 pm, the ZrOSi bond angle is 173.7°.     

Phosphaniminato‐Komplexe des Zirconiums: Die Kristallstrukturen von [ZrCl3(NPPh3)(HNPPh3)2] und [ZrCl2(NPPh3)2(HNPPh3)2]

Phosphoraneiminato Complexes of Zirconium: Crystal Structures of [ZrCl₃(NPPh₃)(HNPPh₃)₂] and [ZrCl₂(NPPh₃)₂(HNPPh₃)₂] The phosphoraneiminato complexes [ZrCl₃(NPPh₃)(HNPPh₃)₂] ( 1 ) and [ZrCl₂(NPPh₃)₂(HNPPh₃)₂] ( 2 ) have been obtained by reaction of [ZrCl₄(THF)₂] with [CsNPPh₃]₄ in THF solution to give colourless moisture sensitive crystals which are characterized by X‐ray structure determinations. [ZrCl₃(NPPh₃)(HNPPh₃)₂] ( 1 ): Space group P 1, Z = 2, lattice dimensions at 193 K: a = 1209.4(2); b = 1480.8(2); c = 1814.2(2) pm; α = 71.203(13)°, β = 71.216(13)°, γ = 74.401(13)°; R = 0.0476. The zirconium atom of 1 is oktahedrally coordinated by the three chlorine atoms in meridional arrangement and by the three nitrogen atoms of the (NPPh₃^–) ligand and of the two phosphane imine molecules HNPPh₃. The ZrN bond distance of the (NPPh₃^–) group (193.5 pm) corresponds with a double bond. [ZrCl₂(NPPh₃)₂(HNPPh₃)₂] ( 2 ): Space group P 1, Z = 4, lattice dimensions at 193 K: a = 1447.6(2); b = 1925.7(2), c = 2457.0(2) pm; α = 67.317(12)°, β = 87.376(12)°, γ = 87.103(13)°; R = 0.0408. The zirconium atom in 2 is octahedrally coordinated by the two chlorine atoms in trans position, and by the nitrogen atoms of the two (NPPh₃^–) groups as well as by the two HNPPh₃ molecules. The ZrN distance of the (NPPh₃^–) ligands (198.9 and 202.0 pm) suggest some π‐interaction between the zirconium and the nitrogen atoms.     

Komplexe von FeI2 und FeI3 mit Tetramethylharnstoff

Complexes of FeI₂ and FeI₃ with Tetramethylurea [FeI₂(OC(NMe₂)₂)₂] ( 1 , [Fe₂I₄(OC(NMe₂)₂)₂] ( 2 ), and [FeI₃(OC(NMe₂)₂] ( 3 ) were prepared by the reaction of FeI₂ and FeI₂/iodine, respectively, with tetramethylurea. The structures of 1 and 3 were determined from single crystal X-ray diffraction data. 1 crystallizes in the triclinic space group P1 , with a = 809.9(1), b = 923.2(1), c = 1 374.6(1) pm, α = 106.80(1), β = 90.47(1), γ = 101.55(1)°; Z = 2; R = 0.045., 3 : monoclinic, P2₁/c, a = 1 311.4(1), b = 783.3(1), c = 1 409.1(1) pm, β = 97.36(1)°; Z = 4; R = 0.047. 1 and 3 are isolated neutral complexes with distorted tetrahedral coordination of iron. 3 is the first FeI₃-complex with an O-donor ligand. The IR-spectra exhibit strong shifts of n?C = O and n?_asC—N of tetramethylurea especially on coordinating to FeI₃.     

Die papierchromatographische und papierelektrophoretische Trennung von einigen Kationen als Komplexe mit Antibiotica

Ohne Zusammenfassung     

Komplexe von Organoblei- und Organozinn-ionen mit 1-(2-Pyridylazo)-2-naphthol

Ohne Zusammenfassung     

Ternäre Komplexe von Eisen(III) mit Ethylendiamintetraessigsäure und Monophenolderivaten

Ternary Complexes of Iron(III) with Ethylene Diamine Tetraacetic Acid and Derivatives of Monophenols Ternary complexes of iron(III) are investigated with ethylenediamine tetraacetic acid and some monophenols in solution as well as their reactions of formation have been controlled by spectrophotometric and elektrophoretic methods. The ratio of components in the compounds Fe: Y: L is 1: 1: 1 without any exception. The measured optical properties (λ_max' ?_max) of the complexes are discussed.     

Die Kristallstrukturen von Triphenylarsin-p-toluolsulfonylimin und seines Donor-Akzeptorkomplexes [ZrCl4(Ph3AsNSO2Tol)]2

The Crystal Structures of Triphenylarsin-p-toluene Sulfonylimine and of its Donor-Acceptor Complex [ZrCl₄(Ph₃AsNSO₂Tol)]₂ The molecular structures of the title compounds are reported. In the donor-acceptor complex [ZrCl₄(Ph₃AsNSO₂Tol)]₂ the zirconium atoms are bridged by the oxygen atoms of the triphenylarsin-p-toluene sulfonylimine molecules, forming a centrosymmetric dimer with a puckered Zr₂O₄S₂ eight-membered ring in the chair conformation. Ph₃AsNSO₂Tol: Space group P1 , Z = 2, structure determination with 4 010 observed unique reflections, R = 0.036. Lattice dimensions at 19°C: a = 897.52(4), b = 1 071.82(6), c = 1 337,49(5) pm, α = 110.280(4)°, β = 98.814(4)°, γ = 109.872(4)°. [ZrCl₄(Ph₃AsNSO₂Tol)]₂: Space group P2₁/n, Z = 4, structure determination with 3 762 observed unique reflections, R = 0.078. Lattice dimensions at ?60°C: a = 1 387.3(4), b = 1 434.9(2), c = 1 404.7(4) pm, β = 92.71(1)°.     

Komplexe von Brenzcatechinviolett mit drei- und vierwertigen Metallen

Ohne Zusammenfassung     

Die Reaktion von Molybdänpentachlorid mit (SCN)2, (SeCN)2 und ICN

Reaction of Molybdenum Pentachloride with (SCN)₂, (SeCN)₂, and ICN By reaction of MoCl₅ with (SCN)₂, (SeCN)₂, and ICN in CCl₄ or H₂CCl₂ the compounds MoCl₅(NCS)₂, MoCl₅(NCSe)₂, and MoCl₅NCI were obtained. They are very sensitive towards hydrolysis and decompose on heating. The compounds are characterized by their vibrational and EPR spectra which indicate that the pseudohalogen is bonded via a nitrogen atom.     

Komplexe von drei- und vierwertigem Nickel mit Stickstoffliganden

Zusammenfassung Die Ni⁴⁺ und Ni³⁺ als Zentralion enthaltenden Komplexe [Ni(C₇H₇N₂O)₄] und [Ni(C₃H₆NO₃)₃] wurden hergestellt und analytisch und magnetometrisch untersucht. Das Tetrabenzamidoximatonickel(IV) ist diamagnetisch und absorbiert bei =490 nm mit einem molaren Extinktionskoeffizienten =3000. Das Triserinonickel(III) ist paramagnetisch mit _eff = 1.71 ± 0.03 [ _B ] und absorbiert bei =536 nm mit =1300.

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Complexes of tri- and Tetravalent Nickel with nitrogen ligands

The complexes [Ni(C₇H₇N₂O)₄] (with benzamidoxime) and [Ni(C₃H₆NO₃)₃] (with serine) containing Ni⁴⁺ and Ni³⁺, resp., as central ions were synthesized and studied analytically and magnetometrically. The tetrabenzamidoximatonickel(IV) is diamagnetic and absorbs at =490 nm with a molar extinction coefficient =3000. The triserinonickel(III) is paramagnetic with _eff = 1.71 ± 0.03 [ _B ] and absorbs at =536 nm with =1300.

     

Phosphaniminato-Komplexe von Titan(IV). Die Kristallstrukturen von [TiCl3(NPEt3)]2, [TiCl3(NPEt3)(THF)2] und [TiCl4{Me2Si(NPEt3)2}]

Phosphoraneiminato Complexes of Titanium(IV). Crystal Structures of [TiCl₃(NPEt₃)]₂, [TiCl₃(NPEt₃)(THF)₂], and [TiCl₄{Me₂Si(NPEt₃)₂}] [TiCl₃(NPEt₃)]₂ ( 1 ) is formed from titanium(IV) chloride and the silylated phosphaneimine Me₃SiNPEt₃ in dichloromethane as reddish-brown, moisture-sensitive crystals. According to the crystal structure analysis these crystals show centrosymmetric Ti₂N₂ four-membered rings with Ti–N distances of 184.7 and 210.3 pm. With tetrahydrofurane 1 forms yellow, moisture sensitive crystals of the solvate [TiCl₃(NPEt₃)(THF)₂] ( 2 ), in which the titanium atom is octahedrally coordinated. The THF molecule which is in trans position to the phosporaneiminato ligand realizes but a very weak Ti–O bond of 238.0 pm, the cis THF molecule shows a Ti–O distance of 213.7 pm. With 173.4 pm along with a TiNP bond angle of 160.0° the TiN distance is very short. The bis(phosphaneimine) complex [TiCl₄{Me₂Si(NPEt₃)₂}] ( 3 ) is formed as colourless crystals in low yield in the reaction of titanium(IV) chloride with Me₃SiNPEt₃ and trimethylcyclopentadienylsilane. In 3 the titanium atom is surrounded by four chlorine atoms in a distorted octahedral fashion and by the two N atoms of the Me₂Si(NPEt₃)₂ molecule with TiN distances of 205.6 pm.     

Die Reaktionen von Dimethylsulfoxid mit Molybdäntetrabromid und Molybdändibromid-dinitrosyl Die Kristallstruktur von [MoBr2(NO)2(OSMe2)2]

Reactions of Dimethyl Sulfoxide with Molybdenum Tetrabromide and Molybdenum Dibromide Dinitrosyl. Crystal Structure of [MoBr₂(NO)₂(OSMe₂)₂] In the cold molybdenum tetrabromide reacts with an equivalent amount of dimethyl sulfoxide forming the solvate [MoBr₄(OSMe₂)₂]; excess dimethyl sulfoxide yields [MoO₂Br₂(OSMe₂)₂] which is also obtained by other methods. Molybdenum dibromidedinitrosyl forms the solvate [MoBr₂(NO)₂(OSMe₂)₂] in the reaction with dimethyl sulfoxide. According to the i.r. spectra all complexes display O-coordination of the OSMe₂ molecules. [MoBr₂(NO)₂(OSMe₂)₂] crystallizes monoclinic in the space group P2₁/c with four formula units per unit cell. The cell dimensions are a = 1236, b = 892, c = 1305 pm, β = 95.2°. 1662 independent observed reflexions were used for refinement; R = 3.8%. The molybdenum atoms are six-coordinated, the O atoms of the dimethyl sulfoxide molecules are in trans-position to the nitrosyl ligands, which form linear groups Mo? N? O.     

Die spektralphotometrische Bestimmung und die Reaktion von Uranylionen mit 4-(2-Thiazolylazo)-resorcin (TAR)

Ohne Zusammenfassung     

Die chelatometrische,photometrische und extraktionsphotometrische Indiumbestimmung mit Hilfe von 1(2-Pyridylazo)4-naphthol

Analytical and Bioanalytical Chemistry -     

Hexakoordinierte Komplexe von Mangan(III) mit Hydrazonen

A few complexes of Mn(III) have been prepared by reacting manganese acetate with aroyl hydrazones in methanolic medium. The elemental analyses indicate 12 or 13 stoichiometry depending on the ligands. On the basis of the physicochemical investigations, coordination number six has been suggested for all these complexes.