Schwingungsspektren und Kraftkonstanten der Übergangsreihe O2PF—S2PF— S2P(CH3)

Vibration spectra and force constants of the series O₂PF — S₂PF — S₂P(CH₃). The vibrational spectra of OSPF, S₂PF, S₂PF(CH₃) and S₂P(CN) are reported and discussed with O₂PF and S₂P(CH₃). On the basis of a simplified valence-force-field the force constants are calculated and the bonding relations are discussed. In the ions, f PF is lower than in corresponding molecules. The ionic charge is distributed over nearly all atoms of the ions.     

Über geordnete Perowskite mit Kationenfehlstellen. XI. Verbindungen vom Typ ABB□1/4WVIO6 ≙ ABIIB□WO24 mit AII,BII = Ba,Sr

On Ordered Perovskites with Cationic Vacancies. XI. Compounds of Type A B B □_1/4W^VIO₆ ? A B^IIB □W O₂₄ with A^II, B^II = Ba, Sr Depending on the ionic radii of the two and three valent cations in the perovskites of type ABB □_1/4W^VIO₆ ?; AB^IIB □WO₂₄ order disorder phenomena are present. The results of the x-ray and vibrational spectroscopic investigations as well as the diffuse reflectance spectra and the visible photoluminescence are reported.     

19F-NMR-spektroskopischer Nachweis und statistische Untersuchung zur Bildung der gemischten Clusteranionen [(Mo6ICl)F]2−, n = 0–7, und Darstellung von (TBA)2[(Mo6I)F]

¹⁹F NMR Spectroscopic Evidence and Calculation of the Statistical Formation of Mixed Cluster Anions [(Mo₆I Cl )F ]^2?, n = 0–7, and Preparation of (TBA)₂[(Mo₆I )F ] The octa-μ₃-iodo-hexafluoro-hexamolybdate(2?)ion [(Mo₆I)F]^2? is prepared for the first time. The system of the 21 innersphere mixed clusters (Mo₆ICl)⁴⁺, n = 0–7 is formed by exchange of innersphere bound Clⁱ against outersphere bound I^a on tempering solid [(Mo₆Cl)I] at 400°C. Prolonged tempering leads to increasing average n values of the mixture, which is converted into the tetrabutylammonium salt (TBA)₂[(Mo₆ICl)F]. Using increments of chemical shifts and integral peak intensities the 54 ¹⁹F-nmr signals of the 21 species (compound n = 8 is absent) are assigned and confirmed by the 2 D-¹⁹F/¹⁹F-COSY spectrum. From the measured intensities the distribution of the different compounds is determined and proves significant deviation from statistical occupation, revealing the preference of isomers with iodine atoms occupying edges of the innersphere cube and discrimination of those sharing diagonals of the faces. Moreover all compounds with n = 3 and 4 are present overaverage in comparison to the others.     

Zur Kristallstruktur von OMF (M = Sb,Ru, Pt,Au)

On the Crystal Structure of O MF (M = Sb, Ru, Pt, Au) OMF (M = Sb, Ru, Pt, Au) were obtained again, but for the first time investigated by X-ray methods. Colourless OSbF and the rubyred compounds ORuF and OPtF crystallize isostructural in space group Ia3 -T_h⁷ (Nr. 206) with a = 1016(1) pm (Sb), a = 1002.6(9) pm (Ru) and a = 1003.6(9) pm (Pt), Z = 8. Yellow OAuF crystallizes trigonal-rhombohedric in space group R3 -D₃₂⁶ (Nr. 148) with a = 775.9(3) pm, c = 711.7(4) pm, Z = 3.     

Über geordnete Perowskite mit Kationenfehlstellen. X. Verbindungen vom Typ ABB□1/4MVIO6 ≙ ABIIB□MO24 mit AII,BII = Ba,Sr, Ca und MVI = U,W

On Ordered Perovskites with Cationic Vacancies. X. Compounds of Type A B B □_1/4M^VIO₆ ? A B^IIB □M O₂₄ with A^II, B^II = Ba, Sr, Ca and M^VI = U, W Perovskites of type Ba₈B^IIB₂^III□UO₂₄ show polymorphic phase transformations of order disorder type. An 1:1 ordered orthorhombic HT form is transformed into a higher ordered LT modification with a fourfold cell content (four formula units Ba₈B^IIB□U₄O₂₄), compared to cubic 1:1 ordered perovskites A₂BMO₆. In the series Ba₈BaB□W₄O₂₄ and Sr₈SrB□W₄O₂₄ different ordering phenomena are observed. In comparison with 1:1 ordered cubic perovskites A₂BMO₆, the cell contains eight formula units AB^IIB□W₄O₂₄. The higher ordered cells with U^VI and W^VI are face centered, which has its origin in an ordering of cationic vacancies.     

Dibrommethylsulfoniumsalze – Darstellung und Kristallstruktur [1]

Dibromomethylsulfoniumsalts — Preparation and Crystal Structure The salts CH₃SBrA^? (A^? = SbCl, AsF) were prepared by various routes and characterized by their Ramanspectra. CH₃SBrAsF crystallized in the monoclinic space group P2₁/c with a = 770,5(4) pm, b = 942,4(12) pm, c = 1329,3(14) pm, β = 100,28(6)°, Z = 4. Distances and bond angles in the cation are as expected.     

19F-NMR-spektroskopischer Nachweis und Berechnung der statistischen Bildung der gemischten Clusteranionen [(Mo6BrCl)F]2−, n = 0 – 8

¹⁹F NMR Spectroscopic Evidence and Calculation of the Statistical Formation of Mixed Cluster Anions [(Mo₆Br Cl )F ]^2?, n = 0 – 8 The complete system of the innersphere mixed clusters (Mo₆BrCl)⁴⁺ is formed by exchange of innersphere bound Clⁱ against outersphere bound Br^a on tempering the solid [(Mo₆Cl)Br] at 500°C for 16 h. After conversion with conc. HCl into (H₃O)₂[(Mo₆BrCl)Cl] and precipitation of the outer Cl^a with AgBF₄ in ethanol, treatment with tetrabutylammonium(TBA)fluoride yields (TBA)₂ [(Mo₆BrCl)F], a mixture of 22 different species. According to the sets of chemical equivalent fluorine atoms in total 55 ¹⁹F nmr signals are expected, which are really observed in the high resolution 1D-¹⁹F-nmr spectrum. Using increments of chemical shifts, peak intensities and multiplet structures as well as the 2D-¹⁹F/¹⁹F-COSY spectrum the complete and unambiguous assignment of all resonances is achieved. From the measured integral intensities the distribution of the different compounds is determined, revealing statistical formation of the geometrical isomers.     

Chemie der Seltenen Erden in geschmolzenen Alkalihalogeniden. XI. Spezifische elektrische Leitfähigkeiten und Aktivierungsenergien von Lanthaniden(III)-jodid–Alkalijodid-Schmelzen

Specific electrical conductivities and activation energies of the molten binary systems RJ₃–MeJ (R = La, Nd, Gd, Dy; Me = Na; K, Cs) have been investigated. In the mixtures with Me = K, Cs there are clear indications to species like RJ, RJ or R₂J.     

Darstellung,Schwingungsspektrum und Kristallstruktur von (n‐Bu4N)2[(W6Cl)F] · 2 CH2Cl2 und 19F‐NMR‐spektroskopischer Nachweis der gemischten Clusteranionen [(W6Cl)FCl]2–, n = 1–6

Synthesis, Vibrational Spectra, and Crystal Structure of ( n ‐Bu₄N)₂[(W₆Cl )F ] · 2 CH₂Cl₂ and ¹⁹F NMR Spectroscopic Evidence of the Mixed Cluster Anions [(W₆Cl )F Cl ]^2–, n = 1–6 The reaction of (n‐Bu₄N)₂[(W₆Cl)Cl] with CF₃COOH in dichloromethane gives intermediately a mixture of the cluster anions [(W₆Cl)(CF₃COO)Cl]^2–, n = 1–6. By treatment with NH₄F the outer sphere coordinated trifluoracetato ligands are easily substituted and the components of the series [(W₆Cl)FCl], n = 1–6 are formed and characterized by their distinct ¹⁹F NMR chemical shifts. An X‐ray structure determination has been performed on a single crystal of (n‐Bu₄N)₂[(W₆Cl)F] · 2 CH₂Cl₂ (orthorhombic, space group Pbca, a = 15.628(4), b = 17.656(3), c = 20.687(4) Å, Z = 4). The low temperatur IR (60 K) and Raman (20 K) spectra are assigned by normal coordinate analysis based on the molecular parameters of the X‐ray determination. The valence force constants are f_d(WW) = 1.89, f_d(WF) = 2.43 and f_d(WCl) = 0.93 mdyn/Å.     

Darstellung und spektroskopische Charakterisierung des Clusteranions [(Mo6Cl8i)(CF3COO)6a]2−

Preparation and Spectroscopic Characterization of the Cluster Anion [(Mo₆Cl )(CF₃COO) ]^2? On heating of [(Mo₆Cl)Cl]^2? in dichloromethane with trifluoroacetic acid the new stable cluster anion [(Mo₆Cl)(CF₃COO)]^2? is formed by elimination of HCl. The (Mo₆Cl) unit remains unattacked. The ¹⁹F nmr spectrum exhibits a downfield shifted singulett as compared to free CF₃COO^? indicating the equivalence of all trifluoroacetate ligands, which unidentate coordination is deduced from characteristic i. r. frequencies of the carboxyl groups. The most intense i.r. band at 501 cm^?1 is assigned to the antisymmetric Mo? O^a vibration, the most intense Raman line at 319 cm^?1 to the breathing mode of the Cl cube.     

Dicyanmethanido- und Cyanamido-oxoanionen. Untersuchungen zum sauerstoffanalogen Charakter der C(CN)2- und NCN-Gruppen

The equivalence of the C(CN)₂- and the NCN-groups with oxygen in the series of homologous ions C(CN), N(CN), OCN^? and NOC(CN), NO causes us to postulate a more general value of this relation. Arguments for the formulation of a pseudochalkogen series C(CN)₂? NCN? O are discussed. Synthesis, structure and reactivity of some dicyanmethanido- and cyanamido-oxoanions RCOY^?, CO₂Y^2?, COY, NOY^?, NO₂Y^?, PO₃Y^3?, PO₂Y and SO₂Y^2? are described. (Y ? C(CN)₂, NCN.) The preparation of some triorganoleadacyles is reported.     

The crystal structure of tris (ethylenediamine), cobalt(III) hexacyanoferrate(III)dihydrate,Co(C2H8N2)3[Fe(CN)6] · 2H2O

The crystal structure of the title compound has been determined from three dimensional x-ray data obtained by the multiple film method. The space group is P2_l/n and the cell dimensions are: a = 14.90, b = 16.84, c = 8.38 Å; β = 93.5° Z = 4. The structure is formed by discrete Co (en) and Fe(CN) ions, both of which have an octahedral configuration. The Fe(CN) ions are approximately octahedrally surrounded by the Co (en) ions while arrangement of Fe (CN) ions around the Co(en) ions completely differs from an octahedron. The mean Fe? C and Co? C dustances are 1.91 and 2.01 Å, respectively. The water molecules do not play an important role in the structure and all distances between oxygen and other atoms indicate the presence of very weak hydrogen bonds. The salts M (en)₃ Q(CN)₆ · H₂O, where M = Co and Cr and Q = Cr, Mn, Fe and Co, are all isomorphous.     

Assembly of Chiral Two- and Three-dimensional Copper(I) Pseudohalide Based Coordination Polymers with Asymmetrically Substituted Pyrazine and Pyrimidine Ligands

The coordination polymers [(CuCN)₂(μ-2 Mepyz)], [CuCN(μ-2 Mepyz)] and [CuCN(μ-4 Mepym)] ( 1 – 3 ) (2 Mepyz = 2-methylpyrazine; 4 Mepym = 4-methylpyrimidine) may be prepared by self-assembly in acetonitrile solution at 100 °C ( 1 , 3 ) or without solvent at 20 °C ( 2 ). All three contain [CuCN] chains that are bridged by the bidentate aromatic ligands into sheets in 1 and 3 D frameworks in 2 and 3 . Reaction of CuSCN with these heterocyclic diazines at 100 °C leads to formation of the lamellar coordination polymers [(CuSCN)(μ-2 Mepyz)] ( 4 ) and [CuSCN · (4 Mepym-κN1)] ( 5 ), which contain respectively [CuSCN] chains and trans-trans fused [CuSCN] sheets as substructures. The presence of an asymmetric substitution pattern in 2 Mepyz and 4 Mepym induces the adoption of a chiral structure by 2 and 5 (space groups P2₁2₁2₁ and P1).     

Über das Auftreten von Monoselenan- und Monotelluran-disulfandiphosphonat bei der Umsetzung von SPO mit Seleno- und Telluropolythionaten

On the Formation of Monoselenane and Monotellurane Disulphane-diphosphonate by the Reaction of SPO with Seleno and Telluropolythionates In the reaction of seleno- and telluropolythionates with SPO, SeS₂P₂O and TeS₂P₂O are formed and are described for the first time. Polysulfphane-diphosphonates, -disulphonates and -phosphonsulphonates occur as side and consecutive products. By evaluation of radiochemical double labelling with the nuclide pairs ³⁵S? ³²P and ³⁵S? ⁷⁵Se, it is possible to identify the products formed and obtain information about the reaction mechanism.     

Thermisches Verhalten und Kristallstruktur von YAl3Cl12

Thermal Behaviour and Crystal Structure of YAl₃Cl₁₂ We determined the thermodynamic data of YAl₃Cl₁₂ ΔH = ?739.9 ± 3 kcal/mol and S = 136.1 ± 4 cal/K · mol by total pressure measurements and ΔH = ?739.1 ± 1.6 kcal/mol by solution calorimetry. Using DTA-investigations we established the phase diagram in the system AlCl₃–YCl₃. The crystal structure was refined on the basis of single crystal data (P3₁ 12; Z = 3; a = 1 046.8(2); c = 1 562.3(3) pm).     

Zur Kenntnis des Verhaltens der Oxidsulfate der Seltenen Erden gegen Chlorwasserstoff. III. Darstellung und thermisches Verhalten der Chloridsulfate der Seltenen Erden

Treatment of chlorination products of rare earths oxidesulphates with methanol yields chloride-sulphates M^IIIClSO₄ as residues. Thermal decomposition of chloride-sulphates yields oxide-sulphates MO₂SO₄; as intermediates, mixtures of the composition MO₂SO₄? M(SO₄)₃ are obtained.     

Subgroup 4 (Ti,Zr, Hf) derivatives of Cobalt Carbonyls

Bimetallic and trimetallic compounds containing unsupported bonds of subgroup 4 metals (M = Ti, Zr, Hf) and Co were prepared by hydride elimination (A) from RM derivatives (R¹ = PhCH₂; RN; R² = Me, Et)) and by salt elimination (B) from RMX (X = Cl, Br; R.¹ = PhCH₂, RN and R³O; R³= i-Pr, n-Bu)) by reaction with HCo(CO)₄ and Na[Co(CO)₄], respectively. Compounds RMCo(CO)₄ with R¹ = PhCH₂, RM[Co(CO)₄]₂ R.¹ = PhCH₂, were prepared both by methods A and B, while (R³O)₄-n Ti[Co(Co)₄]n (n = 1, 2) compounds were obtained by reaction B. Several tertiary phosphine and phosphite derivatives of the former two types were obtained by substitution of a carbonyl group by PR ligand or by A type reaction of HCo(CO)³(PR with RM compounds.     

Silaheterocyklen. III. Erzeugung und Reaktivität von Di-tbutyl-Neopentylsilaethen,BuSiCHCH2But

Silaheterocycles. III. Synthesis and Reactivity of Di-^tbutylneopentylsilaethene, Bu Si?CHCH₂Bu^t The three di-^tbutylvinylsilanes BuSi(X)CH?CH₂ (X = H 5 , X = F 9 , X = Cl 22 ) are prepared by the reaction of their SiCl precursors with vinyl lithium. In the treatment with LiBu^t the first step is the generation of the α-lithio compound BuSi(X)CH(Li)CH₂Bu^t, the following reactions are governed by the nature of the substituent X and the reaction conditions (solvent, concentration, temperature). For X = H 2,3-LiH elimination leads to BuSi(H)CH?CHBu^t ( 7 ), with X = F or Cl Si?C formation by 1,2-LiX elimination competes with intermolecular Si-C-coupling producing BuSi(H)CH(SiBuCH?CHBu^t)CH₂Bu^t ( 13 ) as the main product. BuSi?CHCH₂Bu^t ( 1 ) probably coordinates to LiBu^t and reacts to yield BuSiCH?CHBu^t ( 3 ) and 7 , forms tetrabutyl-dineopentyl-1,3-disilacyclobutane 2 by cyclodimerization and 13 by addition of BuSi(X)CH(Li)CH₂Bu^t.     

Interactions Magnetiques dans quelques Ferrites Oxyfluores a Structure Spinelle de Formule ZnxMFe2−xO4–xFx (M ? Fe,Co, Ni)

Magnetic interactions in some oxyfluoroferrites of spinel structure with the formula Zn_xMe_2?xO_4?xFx (M = Fe, Co, Ni) Whereas the ferromagnetic spin arrangement of the B-cations is not modified by the Zn²⁺?Fe³⁺ substitution in the ZnFe[Fe₂₊Fe³⁺]O_4?xF_x (0 ≤ x ≤ 0,50) spinel, this same substitution leads to a spin canting in the ZnFe[Co₂₊Fe³⁺]O_4?xF_x and ZnFe[Ni₂₊Fe³⁺]O_4?xF_x (0 ≤ x ≤ 0,80) simples. The difference in the magnetic behaviors with regard to the AB and BB interactions can be explained on the basis of the magnetic exchange theory.     

Low Valence States of Metal Chelates. V. Tris(1,10-phenanthroline)cobalt(II) and bis(2,9-dimethyl-1,10-phenanthroline)cobalt(II) perchlorates

D. C. polarography and cyclic voltammetry were used for investigating the reduction processes of the tris(1,10-phenanthroline)cobalt(II) and bis(2,9-dimethyl-1, 10-phenanthroline)-cobalt(II) perchlorates in 0.1 M solutions of tetraethylammonium perchlorate in acetonitrile. The first complex gave a four-step reduction wave; the first two steps were found to be diffusion controlled and reversible reductions from Co(phen)⁺ to Co(phen)₃⁺ to Co(phen) to Co(phen;) occured. The second complex gave a six-step reduction wave; the first three steps were found to be diffusion controlled and were to be considered as successive reversible reductions from Co(2, 9dm-phen)⁺ to Co(2, 9dmphen), from Co(2, 9dmphen) to Co(2, 9dmphen)₂ and from Co(2, 9dmphen)₂ to Co(2, 9dmphen).