Metallkomplexe mit anionischen Liganden von Elementen der 4. Hauptgruppe. XI. Substitutionsreaktionen der Trichlorgermid- und Trichlorstannid-Ionen an Metalltrifluorphosphin-Komplexen

Metal Complexes with Anionic Ligands of Main Group IV Elements. XI. Substitution Reactions of Trichlorogermide and Trichlorostannide Ions with Metaltrifluorophosphine Complexes The photochemical reactions of [SnCl₃]^? in THF with the metal(0)-trifluorophosphine complexes of Ni, Fe, and Mo result in [Ni(PF₃)₃SnCl₃]^?, [Fe(PF₃)₃(SnCl₂]^?, and [Mo(PF₃)₅SnCl₃]^?. [GeCl₃]^?, in substitution reactions not as reactive as [SnCl₃]^?, does react under similar conditions with Fe(NO)₂(PF₃)₂ only, to yield [Fe(NO)₂(PF₃)GeCl₃]^?. With CpMn(PF₃)₃ (Cp = h⁵-C₅H₅) by the intermediatly formed CpMn(PF₃)₂THF both substitution derivatives [CpMn(PF₃)₂ECl₃]^? (E = Ge, Sn) are found. The metallate(0) complexes are isolated as [As(C₆H₅))₄]⁺- and [N(C₂H₅)₄]⁺ -salts; the i.r.- and ¹⁹F-n.m.r.-spectra are reported.     

Metallkomplexe mit anionischen Liganden von Elementen der 4. Hauptgruppe. VII. Über das Substitutionsverhalten von Carbonylnitrosyl-und Nitrosyltrifluorphosphin-Übergangsmetallkomplexen gegenüber Trichlorstannid-Ionen

Metal Complexes with Anionic Ligands of Elements of the Main Group IV. VII(¹) Substitution Reactions of Carbonylnitrosyl and Nitrosyltrifluorophosphine Transition Metal Complexes with Trichlorostannid L-substitution by [SnCl₃]^? occurs if the nitrosyl complexes Co(NO)L₃ and Fe(NO)₂L₂ (L = CO or PF₃) are reacted with [N(C₂H₅)₄][SnCl₃] thermically in tetrahydrofuran as well as photochemically induced in methylenechloride. The complexes Co(NO)L₃ yield the mono-substitution products [N(C₂H₅)₄][Co(NO)L₂SnCl₃], with the iron compounds Fe(NO)₂L₂ only the disubstituted derivative [N(C₂H₅)₄]₂[Fe(NO)₂(SnCl₃)₂] can be isolated. On the other hand CO substitution at (π-C₅H₅)Mo(NO)(CO)₂ by UV irradiation did not suceed both with [SnCl₃]^? and with PF₃. From the IR-spectroscopic data a leastly with PCl₃ comparable π-acceptor ability is derived for the trichlorostannido ligand.     

Metallkomplexe mit anionischen Liganden von Elementen der 4. Hauptgruppe. IX. Zum komplexchemischen Verhalten von Trichlorstannid-und Trichlorgermid-Ionen gegenüber Komplexen von Übergangsmetallen in niedrigen Oxydationsstufen

Metal Complexes with Anionic Ligands of the Main Group IV Elements. IX. Reactions of Trichlorostannide and Trichlorogermide Ions with Complexes of Transition Metals in Low Oxidation States Carhonyl trichlorostannido- and carbonyl trichlorogermido-metalate complexes have been synthesized both by photochemical and thermical substitution reactions of [ECl₃]^? ions (E = Sn, Ge) with M(CO)₆, (M = Cr, Mo, W), Fe(CO)₅ Fe₃(CO)₁₂, Co₂(CO)₈, as well as with the metalcarbonyl derivatives (π-arene)M(CO)₃, (M = Cr, Mo), (h⁵-C₅,H₅,)V(CO)₄, Mn(CO)₅,Cl, Co(NO)(CO)₃, and Fe(NO)₂,(CO)₂. Mainly the bonding properties of the [ECl₃]^? ligands are discussed by means of i.r. spectroscopic investigations. The progress of the reactions and the necessary reaction conditions show that the nucleophilic properties oft both anions [ECl₃]^? are unexpectedly small. The slightly weaker hasicity of [SnCl₃]^? compared with [GeC1₃]^? arreared, when both anions were reacted with Co₂,(CO)₈, forming the substitution product. [Co₂,(CO)₇,SnCl₃]^? and the products of a “base reaction” Cl₃GcCo(CO)₄, and [Co(CO)₄]^?.     

Neue ternäre Phasen von Platinmetallen mit Lithium und Elementen der 4. Hauptgruppe

Novel Ternary Phases of Platinum Metals with Lithium and Main Group IV Elements The elements palladium, platinum, and iridium (Me) form ternary compounds with lithium and the elements germanium, tin or lead (X) of the formulas Li₂MeX and/or LiMe₂X. The lattice constants of the cubic fc. crystallizing compounds see ?Inhaltsübersicht”?. Besides the cubic form of LiPd₂Ge there exists a tetragonal structure with a = 6.25₄ and c = 6.41₀ Å. X-ray investigations on single crystals showed that LiPd₂Ge crystallizes in a Heusler lattice (L2₁A type), Li₂PdSn has a modified Li₃Bi structure (L2₁C type). The homogeneity range between the compositions Li₂PdX and LiPd₂X was investigated.     

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.     

Metallkomplexe mit biologisch wichtigen Liganden,XLV. Palladium(II)-Komplexe mit Dehydro-α-amino- und 2-Iminosäureestern als Liganden

Metal Complexes with Biologically Important Ligands, XLV. — Palladium (II) Complexes of Dehydro-α-amino and 2-Imino Acid Esters as Ligands The preparation and spectroscopic data of the complexes ( 1 ) and ( 6 ) and of [(OC)₅Re H₂NC(CO₂Me)CH(Ph)]⁺ BF ( 2 ) are reported. The reactions of dehydroamino acid esters R(ROC)-CC(CO₂R)NH₂ with Na₂PdCl₄ give 1-imino-3-ketonato chelate complexes ( 3 ), of which one resentative ( 3b ) has been characterized by X-ray structure analysis. For comparison the structure of the dehydroamino acid derivative OC(Me)C(CO₂Et)C(CO₂Et)NH₂ ( 4 ) has also been determined. Palladium(II) binds the anion of dehydroarmentomycin via the N,O atoms ( 8 ). This coordination is also found with (η⁵-C₅H₅)(OC)₂Mo and allylglycinate ( 9 ).     

Ternäre Verbindungen des Lithiums und Natriums mit Mangan und Elementen der 5. Hauptgruppe

Es wird über Darstellung und Kristallstruktur ternärer AMnX-Verbindungen (A ? Li, Na; X ? P, As, Sb, Bi) berichtet. Sie kristallisieren tetragonal in Raumgruppe P4/nmm-D_4h⁷, wobei sich LiMnX und NaMnX durch unterschiedliche Punktlagen der Alkaliatome unterscheiden. Die AMnX-Strukturen werden mit denen verwandter AMX-Verbindungen verglichen (A ? Li, Na, K, Rb; M ? Be, Mg, Zn, Cd; X ? 5b-Element). Ternary Compounds of Lithium and Sodium with Manganese and Elements of the Fifth Main Group Formation and crystal structure of ternary AMnX compounds (A ? Li, Na; X ? P, As, Sb, Bi) are reported. These compounds crystallize in the tetragonal space group P4/nmm-D. The structures of LiMnX and NaMnX differ by the positions of the alkali atoms. Structural relationship to AMX compounds (A ? Li, Na, K, Rb; M ? Be, Mg, Zn, Cd; X ? 5b element) are discussed.     

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.     

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.     

Neue ternäre Verbindungen des Caesiums mit Elementen der 8. Nebengruppe und 5. Hauptgruppe

New Ternary Compounds of Cesium and Elements of the 8^th Transition Metal Group and the 5^th Main Group In the ternary systems Cesium/element of the 8^th transition metal group/element of the 5^th main group some new compounds were found and investigated. Compounds of the formula Cs₂MX₂ (M = Pt, Pd, Ni; X = P, Sb, Bi) can be placed in a line with the K₂PdP₂-type structure. The new compound with the formula CsFe₂Sb₂ crystallizes in the ThCr₂Si₂-type structure. By single crystal measurements CsFe₂As₂ was found to crystallize in the space group I4/mmm with the lattice constants a = 389.43 pm and c = 1 509.97 pm.     

Metall(0)-Komplexe von Nickel und Molybdän mit Benzil-bis-phenyliminen als Chelatliganden

Metal(0) Complexes of Nickel and Molybdenum with Benzil-bis-phenylimines as Chelateligands Benzil-bis-phenylimines form with Mo(CO)6 stable tetracarbonylcomplexes; their spectroscopical behaviour shows, that the ligands are π-electron acceptors. Substitution by R₃P gives tricarbonylcomplexes. Some nickel(0) complexes (NiL₂, Ni(R₃P)L) are described. The magnetical and spectrophotometrical properties of these chelatcomplexes are investigated.     

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°.     

Nickel(O)-Komplexe mit anionischen Liganden des Typs E(C6H5) (E = Si,Ge, Sn)

Nickel(O) Complexes with the Anionic Ligands E (C₆H₅)^?₃ (E = Si, Ge, Sn) Complexes of the type Me^I_XNi(EPH₃)_X(THF)_Y are formed from Ni(COD)₂ by substitution with Me^IEPh₃ (E = Si, Ge, Sn) in THF (COD = Cyclooctadiene-1,5). In the case of the ligands GePh^?₃ and SnPh^?₃ nickel(O) is fourfold coordinated, but in the case of SiPh^?₃ it is only two-fold or threefold coordinated. Products of the reaction between Ni(COD)₂ and LiPbPh₃ are Li₂Ni(COD)Ph₂(THF)₅ and Ph₃PbPbPh₃. The ¹H-n.m.r., ²⁹Si-n.m.r., and ¹¹⁹Sn-Mössbauer spectra of the complexes Me^I_XNi(EPh₃)_X(THF)_Y are compared with the spectra of the corresponding alkali compounds Me^IEPh₃. The magnetic anisotropy effects of the atomes Ge, Sn, Pb and Ni are of high importance for ¹H- and ²⁹Si-chemical shifts. The donor action of SnPh^?₃ is shown by the Mössbauer spectrum of Na₄Ni(SnPh₃)₄(THF)₄. But there is no direct evidence of π-back donation in the compound.     

Katalytisch-kinetische bestimmung von katalase, kupfer, molybdän und jodid mit hilfe eines biamperostaten

Biamperometrically observable reactions may be evaluated by the “potentiostat”-method with the application of a current-to-voltage transducer. The catalase-catalyzed autodecomposition of hydrogen peroxide, the copper-catalyzed oxidation of iodide with peroxydisulfate, the molybdenum(VI)-catalyzed oxidation of iodide with hydrogen peroxide, and the iodide-catalyzed oxidation of arsenic(III) with cerium(IV) are used to illustrate this concept. The catalysts, catalase, copper(II), molybdenum(VI) and iodide, as well as azide as an inhibitor for catalase, can be determined in the p.p.b.-p.p.m. range.     

Cyanato-Kupfer(II)-Komplexe mit organischen Liganden, 3. Mitt.: Darstellung,magnetische Suszeptibilität und Elektronenspektren der Cyanato-Kupfer(II)-Komplexe mit methylsubstituierten Pyridinen

Zusammenfassung Neue Cyanato-Kupfer(II)-Komplexe des Typs Cu(NCO)₂ L ₂ wurden bereitet, wobeiL -, - bzw. -Picolin, 2,4-Lutidin, 2,6-Lutidin oder 2,4,6-Collidin bedeutet; ferner Komplexe des Typs Cu(NCO)₂ L, wobeiL -Picolin oder 2,4-Lutidin ist. Ihre magnetische Suszeptibilität wurde bei verschiedenen Temperaturen gemessen und ihre Diffusions-Reflexionsspektren wurden dargestellt. Auf Grund der ermittelten magnetischen und spektralen Daten wird den Komplexen Cu(NCO)₂ L ₂ tetragonale Struktur verschiedenen Distorsionsgrades zugesprochen; der sterische Effekt der -methylsubstituierten LigandenL wird diskutiert. Die magnetischen und spektralen Eigenschaften der Komplexe Cu(NCO)₂ L hingegen deuten auf eine ungewöhnliche Art der Koordination.

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Cyanato copper(II) complexes with organic ligands, III: Preparation, magnetic susceptibility, and electronic spectra of the cyanato copper(II) complexes with methyl substituted pyridines

New cyanato copper complexes of the type Cu(NCO)₂ L ₂ have been prepared, whereL represents -, - or -picoline, 2.4-lutidine, 2.6-lutidine or 2.4.6-collidine. In a further series of complexes, Cu(NCO)₂ L, L represents -picoline or 2.4-lutidine. Their magnetic susceptibilities were determined at various temperatures and their diffusion-reflection spectra measured. On the basis of these data a tetragonal structure with varying degrees of distortion is assigned to the complexes Cu(NCO)₂ L ₂, and the steric effect of the -methyl-substituted ligandsL is discussed. The magnetic and spectral properties of the complexes Cu(NCO)₂ L indicate, however, a rather unusual kind of coordination.

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Mit 4 Abbildungen

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Teil der Habilitationsschrift vonJ. Kohout, Slowakische Technische Hochschule, Bratislava 1970.