Beiträge zur Chemie der Silicium-Schwefel-Verbindungen. 47 [1]. Über die protolytische Spaltung der Si?S-Bindung in Trialkoxysilanthiolen und Darstellung von Trialkoxyorganoxysilanen

Contributions to the Chemistry of Silicon-Sulphur Compounds. 47. On Protolytic Splitting of the Si? S Bond of Trialkoxysilanethiols and Preparation of Trialkoxyorganoxysilanes The conditions of the reaction of protolytic splitting of the Si? S bond of (RO)₃SiSH by alcohols or phenols were optimized by use of pyridine. Some new trialkoxyorganoxysilanes have been prepared. By kinetic measurements the relationship between the structure of phenol and reaction rate were elucidated. The role of pyridine in the reaction mechanism has been proposed as nucleophile catalysis.     

Untersuchungen über die Alkoholyse des SiS2. VII Die Acidität der Trialkoxysilanthiole

Studies on the Alcoholysis of SiS₂. VII. The Acidity of Trialkoxysilanethiols. The relative acidities of trialkoxysilanethiols (RO)₃SiSH were determined by means of potentiometric titration.     

Beiträge zur Chemie der Silicium-Schwefel-Verbindungen. XLIII. Alkoholyse von Silicium-Schwefel-Verbindungen mit Alkoxyethanolen und 2-Mercaptoethanol

Contributions to the Chemistry of Silicon-Sulphur Compounds. XLIII. Alcoholysis Reaction of Silicon-Sulphur Compounds with Alkoxyethanols and 2-Mercaptoethanol The reactions of 2-alkoxyethanols und 2-mercaptoethanol with (RO)₃SiSH, (RO)₂Si(SH)₂, cyclo-[(t-BuO₂)SiS]₂, and SiS₂ were investigated. Besides of mixed esters of orthosilicic acid a new group of mixed trialkoxysilanethiols – (RO)₂(R′O)SiSH – was obtained. Informations about the hydrolytic splitting of the Si? S bond of these Si? S compounds were obtained by thiomercurimetric titration with HMB.     

Beiträge zur Komplexchemie der Phosphine und Phosphinoxide. XXIII. Schwermetallkomplexe des Tetramethyl-biphosphins

On the coordination chemistry of phosphines and phosphinoxides. XXIII. Heavy metal complexes of tetramethyl-biphosphine The reactions of tetramethyl-biphosphine with salts of 3d elements including Cd and Hg, too, in THF, benzene, acetonitrile and alcohols, respectively, results in forming complexes of differing compositions: (MⁿX_n)₂{(CH₃)₂P? P(CH₃}₂)₃? Mⁿ = Ti^III, V^III, Cr^III, Fe^II, Ni^II, Cu^I; MX₂{(CH₃)₂P? P(CH₃)₂}₂? M = Co^II, Ni^II, Hg^II; MX₂ · (CH₃)₂P? P(CH₃)₂? M = Fe^II, Ni^II, Zn, Cd, Hg^II; X = Cl, Br, J. The partly intensively coloured complexes have low solubilities; this item complicates the performing of structure determining methods. Partial informations about the structures of the complexes are to be gained by magnetic and spectrophotometric measurements and X-ray investigations. The tendency of (CH₃)₂P? P(CH₃)₂ to form complexes with transition metals differs from that of other biphosphines. Splitting of the P? P bond due to metal salts does not occur. (CH₃)₂P? P(CH₃)₂ acts as a monodentate or bidentate ligand, like other members of the R₂P? PR₂ series do too. The forming of ligand bridges seems to be favoured in comparison to the chelate function.     

Beiträge zur Chemie der Silicium-Schwefel-Verbindungen. XLIX. Reaktion von Silicium-Schwefel-Verbindungen mit Glykolen

Contribtions to the Chemistry of Silicon-Sulphur Compounds. XLIX. Reaction of Silicon-Sulphur Compounds with Glycols The reactions of Ph₃SiSH, (RO)₃SiSH, (RO)₂Si(SH)₂, cyclo-[(t-BuO)₂SiS]₂, and SiS₂ with aliphatic glycols were investigated. Among other compounds representatives of a new group of silanethiols (t-BuO)₂Si(SH)OrOSi(SH)(OBu-t)₂ (r = pr; neopent)

1 r = kohlenwasserstoffgerüst des Glykols: pr = ? CH₂CH₂CH₂? , bu = ? CH₂(CH₂)₂CH₂? , hex = ? CH₂(CH₂)₄CH₂? , neopent = ? CH₂C(CH₃)₂CH₂? , pin = ? C(CH₃)₂C(CH₃)₂?

were obtained. Informations about the hydrolytic splitting of the Si? S bond of the prepared silanethiols were obtained by thiomercurimetric titration. A pathway of the reaction of SiS ₂ with glycols is discussed.     

Beiträge zur Chemie der Silicium-Schwefel-Verbindungen. XXIII. Die Hydrolysereaktion der Silanthiole

Contributions to the Chemistry of Silicon-Sulphur Compounds. XXIII. The Hydrolysis Reaction of Silanethiols The kinetics of the hydrolysis reaction of silanethiols (RO)₃SiSH and R₃SiSH in dioxane-water solutions were investigated and the rate constants and the activation parameters evaluated. The mechanism of the reaction is discussed. The relationship between the structure of silanethiols and their reactivity are evaluated.     

Beiträge zur Chemie der Silicium-Schwefel-Verbindungen. 44. Trialkoxysilylthioderivate der Permethylpolysilane

Contributions to the Chemistry of Silicon-Sulphur Compounds. 44. Trialkoxysilylthio Derivatives of Permethylpolysilanes By reaction of (RO)₃SiSH · NEt₃ (R = i-Pr, t-Bu) with α,ω-Cl₂(SiMe₂)_n (n = 1, 2, 3, 4, 6) or with 1-Cl(SiMe₂)_nMe (n = 2, 4) trialkoxysilylthio derivatives of polysilanes of the two series α,ω-(RO)₃SiS(SiMe₂)_nSSi(OR)₃ and 1-(RO)₃SiS(SiMe₂)_nMe have been prepared. Some properties of obtained new compounds were given. The resistance of the Si? S bond on protolytic splitting has been characterized by half-life times of the alcoholysis reaction.     

Zur Frage der Isomorphie der Wasserfreien Doppelsulfate von CuII

On the Isomorphism of Anhydrous Double Sulphates of Cu^II Structural properties of MCu(SO₄)₂ (where M^I = Na, K, Rb, Cs and Tl) compounds were studied, using their i.r. spectra and X-ray powder diffractograms. It was found that the compounds, unlike their hexa- or dihydrates, are not isomorphous. This result is consistent with i.r. data, which show that the bonding mode of the sulphate groups is different for various M^I.     

Die Kristallstrukturen der Vanadium-Weberite Na2MIIVIIIF7 (MII  Mn,Ni, Cu) und von NaVF4

The Crystal Structures of the Vanadium Weberites Na₂M^IIV^IIIF₇ (M^II ? Mn, Ni, Cu) and of NaVF₄ At single crystals of the vanadium(III) compounds NaVF₄ (a = 790.1, b = 531.7, c = 754.0 pm, β = 101.7°; P2₁/c, Z = 4), Na₂NiVF₇ (a = 726.0, b = 1031.9, c = 744.6 pm; Imma, Z = 4) and Na₂CuVF₇ (a = 717.6, b = 1043.5, c = 754.6 pm; Pmnb, Z = 4) X-ray structure determinations were performed, at Na₂MnVF₇ (a = 746.7, c = 1821.6 pm; P3₂21, Z = 6) a new refinement. NaVF₄ crystallizes in the layer structure type of NaNbO₂F₂. The fluorides Na₂M^IIVF₇ represent new orthorhombic (M^II ? Ni; Cu) resp. trigonal (M^II ? Mn) weberites. The average distances within the [VF₆] octahedra of the four compounds are in good agreement with each other and with data of related fluorides (V? F: 193.3 pm). The differences between mean bond lengths of terminal and bridging F ligands are 5% in NaVF₄, but less than 1% in the weberites. Details and data for comparison are discussed.     

Neue Redoxserien auf der Basis von Übergangsmetallkomplexen heterocyclischer Arensulfonylhydrazone

New Redox Series Based on Transition Metal Complexes of Heterocyclic Arenesulfonylhydrazones Heterocyclic bidentate arenesulfonylhydrazones (2-acetylpyridine-p-toluenesulfonylhydrazone ? APSH? H, 2-acetylquinoline-p-toluenesulfonylhydrazone ? ACSH? H) with transition metal ions afford tetrahedral 1,2-complexes M^II(APSH)₂ and M^II(ACSH)₂. In most cases the E-isomers of APSH^? and ACSH^? are coordinated, five-membered chelate rings are formed with the pyridine and hydrazone nitrogen atoms as donor atoms. In the complexes Zn(APSH)₂ and Cu(APSH)₂ probably the Z-isomer of APSH^? is present with the pyridine and the sulfonylamide nitrogen atoms as a donor set, yielding a six-membered chelate ring. These proposals are based on the magnetic moments, the ligand field spectra, and the binding energies (ESCA). Normally the complexes M^II(APSH)₂ and M^II(ACSH)₂ are reduced in two reversible steps. For Fe(APSH)₂ and Fe(ACSH)₂ a third anodic wave, but for Cu(APSH)₂ only one wave is observed. Relations between redox properties and structure of the new complexes are discussed, and the redox series are compared with that of the M(dipy)₃ⁿ⁺-type complexes.     

Die binuklearen Produkte der Umsetzung von Grignardreagenzien mit Acetylacetonaten der späten 3d-Elemente und ihre katalytische Wirkung bei der Kreuzkopplung

Binuclear Reaction Products of Grignard Compounds and Transition Metal Acetylacetonates - Catalysts of Cross Coupling In THF Grignard compounds react with transition metal acetylacetonates forming the binuclear complexes (THF)₂Mg(acac)₂M^IIX₂ (M^II ? Fe, Co, Ni; X ? Cl, Br). A characteristic component of these compounds is the octahedral moiety (THF)₂Mg(acac)₂. The coordination of two cis-positioned oxygen donors of this moiety to an M^IIX₂-group builds up a second (tetrahedral) coordination centre. The structure of the binuclear complexes and their vis-spectra are discussed in detail. The new compounds are cross coupling catalysts of acylhalides and Grignard reagents. Probably in the course of the catalytic process the acylhalides are activated at the unsaturated transition metal centre (increase of the coordination number), but the Grignard reagent at the magnesium centre (substitution of one of the weakly bound THF-ligands). This model also explains the different catalytic activity of (THF)₂Mg(acac)₂FeCl₂ and (THF)₂Mg(acac)₂NiBr₂.     

Jahn-Teller-Verzerrungen von Übergangsmetallionen in tetraedrischer Koordination – die Strukturen von Cat[MII(NCS)4] (MII: Co,Ni, Cu) und von Spinellmischkristallen MIICr2O4(MII: Zn?Ni,Zn?Cu,Cu?Ni)

Jahn-Teller Distortions of Transition Metal Ions in Tetrahedral Coordination — The Structures of Cat[M^II(NCS)₄]^II (M^II: Co, Ni, Cu) and of Mixed Crystals M^IICr₂O₄(M^II: Zn? Ni, Zn? Cu, Cu? Ni) of the Spinel Type The structure determination of compounds Cat[M^II(NCS)₄] with Cat = p-xylylenebis(triphenylphosphonium)²⁺ and M^II = Co, Ni, Cu [space group P2₁/n, Z = 4] yielded pseudotetrahedral M^IIN₄-polyhedra, which are distorted by packing forces and vibronic coupling effects of the Jahn-Teller type. Spinel mixed crystals with M^II = Zn? Ni, Zn? Cu, Ni? Cu in the tetrahedral sites exhibit phase transition to tetragonal and o-rhombic structures, induced by cooperative Jahn-Teller interactions. The distortion symmetries of the M^IIN₄ and M^IIO₄ tetrahedra are analysed on the basis of the respective electronic groundstate and the possible Jahn-Teller active vibrational modes.     

Darstellung,Schwingungsspektren und Struktur von Oxotetrafluorovanadaten MIVOF4 (MI = Na,K, Rb,Cs, Tl, (CH3)4N)

Preparation, Vibrational Spectra, and Structure of Oxotetrafluorovanadates M^IVOF₄ (M^I = Na, K, Rb, Cs, Tl, (CH₃)₄N) The compounds M^IVOF₄ (M^I = K, Rb, Cs, Tl) and M^IVOF₄ · H₂O (M^I = Na, (CH₃)₄N) have been prepared. The crystal structure of KVOF₄ has been determined by single crystal X-ray diffraction. The VOF-ions form endless chains by fluorine bridges. The lengths of the bridge bonds are 1.875(7) and 2.333(7) Å. The terminal V? O- and V? F-distances are 1.572(8) and 1.793 Å (mean value), respectively. The vibrational spectra have been registered and assigned.     

Über Usovite Ba2M″ M″ M2″ F14 und die Hochdruckphasen von BaMnVF7 und BaMnFeF7: Verbindungen mit BaMnGaF7-Struktur

On Usovites Ba₂M^IIM′^IIM₂^IIIF₁₄ and the High Pressure Phases of BaMnVF₇ and BaMnFeF₇: Compounds with BaMnGaF₇ Structure The results of complete single crystal structure determinations of the monoclinic BaMnGaF₇ type compounds Ba₂CaCoV₂F₁₄ (and Ba₂CdMn Fe₂F₁₄) are reported: C2/c, Z = 4, a = 1369.7 (1381.2), b = 538.4 (537.2), c = 1491.6 (1489.5) pm, β = 91.49 (91.11)°, Rg = 0.036 (0.038) for 4389 (2521) reflections. The atoms Ca/Co (Cd/Mn) distribute not completely ordered on the 8? and 6?coordinated sites of this “usovite” structure (Ba₂CaMgAl₂F₁₄). This is also evident for Cd/Fe from Mössbauer spectra of Ba₂CdFeAl₂F₁₄. The lattice constants of this and further seven compounds Ba₂M^IIM′^IIM2_IIIF₁₄ (M^II = Ca, Cd; M′^II = Mg, Mn? Cu; M^II = Al, Ga) are given. Two novel representatives of the same structure with M^II = M′^II = Mn could be prepared in the form of the high pressure phases of BaMn VF₇ and BaMnFeF₇. The magnetic properties of both modifications of the iron compound and of BaMnGaF₇ are reported and discussed.     

Bildung von Chelat-Liganden aus Pseudohalogenid und Pyrazol in der Koordinationssphäre von PdII und PtII

Formation of Chelate Ligands from Pseudohalide and Pyrazole in the Coordination Sphere of Pd^II and Pt^II New Pd^II and Pt^II complexes of the composition M(L · X)₂ were prepared (X = NCO^?), N(CN), C(CN), L = pyrazole (Pz), 3, 5-dimethylpyrazole (Dmpz) and studied applying IR spectroscopy. The complexes are obtained by nucleophilic addition of imine nitrogen from the pyrazole ring to the carbon from the pseudohalide anion. When the neutral ligand was Dmpz the reaction ran partially anly. With NCS^? and pz only the complex Cu(NCS)₂(Pz)₂ is yield.     

Darstellung und Kristallstruktur von K4[SnO3]

Preparation and Crystal Structure of K₄[SnO₃] K₄[SnO₃] crystallizes with the K₄[PbO₃] structure in the orthorhombic spacegroup Pbca (No. 61) with the lattice constants a = 652.2(3) pm, b = 1 112.1(5) pm and c = 1 893.7(7) pm. In the structure isolated ψ-tetrahedral anions [Sn^IIO₃]^4? are arranged in layers perpendicular [001]. The structure of K₄[SnO₃] will be compared with those of stannates and plumbates of composition A₄[M^IIO₃] (A = Na, K, Rb, Cs) and with the known potassium stannates(II).     

Thermolyse von Cyanokomplexen. VII. Über die Thermischen Zersetzungsreaktionen der Hexacyanokobalte(III); Ligandenumlagerungen bei der Thermolyse

Thermolysis of cyano complexes. VII. On the thermal decomposition of hexacyanocobaltate(III); ligand exchange during thermolysis The thermal decomposition of hexacyanocobaltates(III) yields, as products of successive intramolecular redox reactions, first dicyan and Co^II(Co^III)-complexes, then Co^II[Co^II]-complexes and simple Co^II(CN)₂, respectively, and finally Co^ICN and elemental Co, respectively. All the compounds of the [Co^III(NH₃)₆]³⁺ cation with the cyanometallate anions of Co, Fe, Cr, Mn, Ni, Mo yield the same DTA curve as [Co(NH₃)₆][Co(CN)₆] does; in the case of Ni and Cr, which are capable of forming ammine complexes, simultaneous mutual ligand exchange occurs.     

Darstellung von oligomeren und polymeren Alkali-Aluminium- und Alkali-Eisen-Phosphaten

Synthesis of Oligomeric and Polymeric Alkali Aluminium and Alkali Iron Phosphates By thermal reactions in surplus phosphoric acid in dependence on the temperature, the size of the alkali cations M^I and the atomic ratio M^I:M^III alkali aluminium and alkali iron phosphates are formed, which with regard to the structure of their anions belong to seven different types of compounds. Compounds of the type M^IM [(H₂P₃O₁₀)(P₄O₁₂)] were obtained for the first time. The crystal lattice of these compounds includes both linear triphosphate and cyclotetraphosphate anions.     

Beiträge zur Komplexchemie der Phosphine und Phosphinoxide. XXXI. Cobalt- sowie Rhodiumkomplexe primärer Mercaptoalkylphosphine und Bemerkungen zur Komplexbildung quadridentater P,P,S,S-Liganden

On the Coordination Chemistry of Phosphines and Phosphinoxides. XXXI. Cobalt and Rhodium Complexes of Primary Mercaptoalkylphosphines and Remarks on the Complex Formation of Quadridentate P,P,S,S Ligands Primary Mercaptoalkylphosphines (H₂P? CH₂ · CH₂? SH; H₂P? CH₂ · CHCH₃? SH) react with d⁷-metal salts to give octahedron 1:3 chelat complexes. In case of cobalt the oxidation of Co^II to Co^III are obtained by formation of H₂. Structure and properties of these complexes as well as their reactivity like S-alkylation or metallation with following reactions are described. Reaction scheme see ?Inhaltsübersicht”?. With quadridentate ligands HS+ +PH+ +PH+ +SH = L result chelat-complexes of the type [M^III? L XNH₃] (M = Co, Rh) and such as [M^II? L] (M = Ni, Pd, Pt).     

Darstellung und Charakterisierung von Iodoplatinaten MexNH4–xPtI4 (x = 2 − 4), gemischtvalenten Octaiododiplatinaten(II,IV) mit Pt2I8-Baugruppen

Preparation and Characterization of Iodoplatinates Me_xNH_4–xPtI₄ (x = 2–4), Mixed Valence Octaiododiplatinates(II,IV) with Pt₂I₈ Groups Iodoplatinates APtI₄ (A = Me_xNH_4–x with x = 2–4) have been prepared by partial oxidation of the correspondent hexaiododiplatinates(II) A₂Pt₂I₆ with I₂ in methanolic solutions. X-ray structure analyses of the bronze-coloured needle-shaped crystals of the compounds showed rows of dinuclear anions Pt₂I₈^2?, built up by edgesharing planar PtI₄ groups with Pt^II und octahedral PtI₆ groups with Pt^IV. The different space requirement of the cations leads to the formation of three different structures. Within the anion stacks weak intermolecular Pt^IV? I …? Pt^II interactions are detectable by Raman spectroscopy.