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.     

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.     

Darstellung,Kristallstrukturen und Schwingungsspektren von [(Mo6X)Y]2–; Xi = Cl,Br; Ya = NO3, NO2

Synthesis, Crystal Structures, and Vibrational Spectra of [(Mo₆X)Y]^2–; Xⁱ = Cl, Br; Y^a = NO₃, NO₂ By treatment of [(Mo₆X)Y]^2–; Xⁱ = Y^a = Cl, Br with AgNO₃ or AgNO₂ by strictly exclusion of oxygene in acetone the hexanitrato and hexanitrito cluster anions [(Mo₆X)Y]^2–, Y^a = NO₂, NO₃ are formed. X-ray structure determinations of (Ph₄As)₂[(Mo₆Cl)(NO₃)] · 2 Me₂CO ( 1 ) (monoclinic, space group P2₁/n, a = 12.696(3), b = 21.526(1), c = 14.275(5) Å, β = 115.02(2)°, Z = 2), (n-Bu₄N)₂[(Mo₆Br)(NO₃)] · 2 CH₂Cl₂ ( 2 ) (monoclinic, space group P2₁/n, a = 14.390(5), b = 11.216(5), c = 21.179(5)Å, β = 96.475(5)°, Z = 2) and (Ph₄P)₂[(Mo₆Cl)(NO₂)] (3) (monoclinic, space group P2₁/n, a = 11.823(5), b = 13.415(5), c = 19.286(5) Å, β = 105.090(5)°, Z = 2) reveal the coordination of the ligands via O atoms with (Mo–O) bond lengths of 2.11–2.13 Å, and (MoON) angles of 122–131°. The vibrational spectra of the nitrato compounds show the typical innerligand vibrations ν_as(NO₂) (∼ 1500), ν_s(NO₂) (∼ 1270) and ν(NO) (∼ 980 cm^–1). The stretching vibrations ν(N=O) at 1460–1490 cm^–1 and ν(N–O) in the range of 950–1000 cm^–1 are characteristic for nitrito ligands coordinated via O atoms.     

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.     

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.     

Darstellung,Schwingungsspektren und Kristallstrukturen von [(Ph3P)2N]2[(W6Cl)I] · 2 Et2O · 2 CH2Cl2 und [(Ph3P)2N]2[(W6Cl)(NCS)] · 2 CH2Cl2

Synthesis, Crystal Structures, and Vibrational Spectra of [(Ph₃P)₂N]₂[(W₆Cl )I ] · 2 Et₂O · 2 CH₂Cl₂ and [(Ph₃P)₂N]₂[(W₆Cl )(NCS) ] · 2 CH₂Cl₂ By treatment of [(W₆Cl)I]^2– with (SCN)₂ in dichloromethane at –20 °C the hexaisothiocyanato cluster anion [(W₆Cl)(NCS)]^2– is formed. X‐ray structure determinations have been performed on single crystals of [(Ph₃P)₂N]₂[(W₆Cl)I] · 2 CH₂Cl₂ · 2 Et₂O ( 1 ) (triclinic, space group P1, a = 10.324(5), b = 14.908(3), c = 17.734(8) Å, α = 112.78(2)°, β = 99.13(3)°, γ = 92.02(3)°, Z = 1) and [(Ph₃P)₂N]₂[(W₆Cl)(NCS)] · 2 CH₂Cl₂ ( 2 ) (triclinic, space group P1, a = 11.115(2), b = 14.839(2), c = 17.036(3) Å, α = 104.46(1)°, β = 105.75(2)°, γ = 110.59(1)°, Z = 1). The thiocyanate ligands of 2 are bound exclusively via N atoms with W–N bond lengths of 2.091–2.107 Å, W–N–C angles of 173.1–176.9° and N–C–S angles of 178.1–179.3°. The vibrational spectra exhibit characteristic innerligand vibrations at 2067–2045 (ν_CN), 879–867 (ν_CS) and 490–482 (δ_NCS). Based on the molekular parameters of the X‐ray determination of 1 the vibrational spectra of the corresponding (n‐Bu₄N) salt of 1 are assigned by normal coordinate analysis. The valence force constants are f_d(WW) = 1.61, f_d(WI) = 1.23 and f_d(WCl) = 1.10 mdyn/Å.     

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.     

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).     

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.     

Darstellung,Kristallstrukturen und Schwingungsspektren von [OsBr(acac)(PPh3)] und [OsBr(acac)(AsPh3)]

Synthesis, Crystal Structures, and Vibrational Spectra of [OsBr(acac)(PPh₃)] and [OsBr(acac)(AsPh₃)] By reaction of tetrabromoacetylacetonatoosmate(IV) with PPh₃ or AsPh₃ in ethanol the complexes [OsBr(acac)(PPh₃)] ( 1 ) and [OsBr(acac)(AsPh₃)] ( 2 ) are formed, which are purified by chromatography on silica gel. X-ray structure determinations of single crystals of ( 1 ) (monoclinic, space group P 2₁/n, a = 13.035(2), b = 18.2640(14), c = 16.636(3) Å, β = 112.776(14)°, Z = 4) and ( 2 ) (monoclinic, space group P 2₁/c, a = 13.23(5), b = 18.35(2), c = 16.65(2) Å, β = 112.9(5)°, Z = 4) result in mean bond distances Os–P = 2.413, Os–As = 2.483, Os–Br = 2.488 and Os–O = 2.037 Å. The vibrational spectra (10 K) exhibit the inner ligand vibrations of the acac, PPh₃ and AsPh₃ groups with nearly constant frequencies and the stretching vibrations of OsP at 499–522, of OsAs at 330–339, of OsBr at 213–214 and of OsO in the range 460–694 cm^–1.     

Bis[N-(trimethylsilyl)iminobenzoyl]phosphanide des Lithiums und Zinks – Synthese sowie NMR-spektroskopische,strukturelle und quantenchemische Untersuchungen

Acyl- and Alkylidenephosphanes. XXXV. Bis[ N -(trimethylsilyl)iminobenzoyl]phosphanides of Lithium and Zinc – Syntheses as well as NMR Spectroscopic, Structural, and Quantumchemical Studies From the reaction of bis(tetrahydrofuran)lithium bis(trimethylsilyl)phosphanide with two equivalents of benzonitrile in 1,2-dimethoxyethane, the yellow dme complex ( 2 a ) of lithium bis[N-(trimethylsilyl)iminobenzoyl]phosphanide ( 2 ) was obtained in 69% yield. However, the intermediate {1-[N-lithium-N-(trimethylsilyl)amido]benzylidene}trimethylsilylphosphane ( 1 ), formed by an analogous 1 : 1 addition in diethyl ether, turned out to be unstable and as a consequence could be characterized by nmr spectroscopic methods only; attempts to isolate the compound failed, but small amounts of the neutral complex 2 b , with the ligands benzonitrile and tetrahydrofuran coordinated to lithium, precipitated. The reaction of compound 2 with zinc(II) chloride in diethyl ether gives the orange-red spiro-complex zinc bis{bis[N-(trimethylsilyl)iminobenzoyl]phosphanide} ( 3 ); this complex is also formed from bis[N-(trimethylsilyl)iminobenzoyl]phosphane ( 4 ), easily amenable by a lithium hydrogen exchange of 2 a with trifluoroacetic acid [18], and zinc bis[bis(trimethylsilyl)amide]. As derived from nmr spectroscopic studies and x-ray structure determinations, compounds 2 a {δ³¹P +63.3 ppm; P2₁/n; Z = 4; R₁ = 0.067}, 2 b {δ³¹P +63.3 ppm; P2₁/c; Z = 4; R₁ = 0.063}, 3 {δ³¹P +58.2 ppm; C2/c; Z = 4; R₁ = 0.037} and 4 {δ³¹P +58.1 ppm [18]} exist as cyclic 3-imino-2λ³σ²-phosphapropenylamides and -propenylamine, respectively, in solution as well as in the solid state. Unlike hydrogen derivative 4 the bis[N-(trimethylsilyl)iminobenzoyl]phosphanide fragments N,N′-coordinating either a lithium or a zinc cation are characterized by almost completely equalized bond lengths; typical mean distances and angles are: PC 180.3 and 178.7; CN 130.5 and 131.8; N–Si 175.3 and 179.3; N–Li 202.3; N–Zn 203.5 pm; CPC 108.8° and 110.5°; PCN 130.9° and 132.9°; CN–Li 113.0°, CN–Zn 117.4°; N–Li–N 104.6°; N–Zn–N 108.8°. Alterations in the shape of the six membered chelate rings, caused by an exchange of the 3-imino-2λ³σ²-phosphapropenylamide or related 2λ³σ²-phospha-1,3-dionate units for the corresponding phosphorus free ligands, are discussed in detail. The results of quantumchemical DFT-B3LYP calculations coincide very well with the experimentally obtained findings.     

Über das Auftreten von Polysulfan-diphosphonaten bei der Umsetzung von Monothiophosphat mit Disulfan-diphosphonat

On the Formation of Polysulphane Diphosphonates by the Reaction of Monothiophosphonate with Disulphane Diphosphonate In acid solution SPO reacts with S₂P₂O forming higher polysulphane diphosphonates. The formation of S₃P₂O and S₄P₂O is proved by evaluation of the double labelling with ³⁵S? ³²P after high paper electrophoresis.     

Vorberichte angenommener Arbeiten

On the Formation of Polysulphane Phosphonsulphonates by the Reaction of SPO with Polythionates and S₂O with Disulphane Diphosphonate Polysulphane diphosphonates and polysulphane phosphonsulphonates are formed in the reaction of SPO and polysulphane disulphonates in acid solution. The polysulphane phosphonsulphonates are described here for the first time. The same products yielded when S₂O reacts with S₂P₂O. The formation of these compounds depends on nucleophilic attack of the SPO on the sulfur chains of the starting materials, during which growth of the sulfur chains partly occurs.     

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.     

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.     

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).     

Neutral and Cationic Hexanuclear Rhenium Phosphine Clusters with μ3‐(Phosphido‐Chalcogenido), μ3‐(Arsenido‐Chalcogenido), and μ3‐(Imido or Oxo‐Chalcogenido) Hetero Ligand Shells

Reactions of dry THF/MeCN solutions of Ca[Re₆SCl(Cl^a)₆] with silylated derivatives E(SiMe₃)₂ (E = PhAs, PSiMe₃, HN, O, S) and addition of trialkylphosphine PPr₃ afford in high yields and at room temperature either the neutral clusters [Re₆SX(PPr₃)] ( 1 : X = As, 2 : X = P) or the ionic compounds [Re₆SX(PPr₃)]²⁺ · [Re₆S₆Cl₈]^2– ( 3 : X = NH, 4 : X = O, 5 : X = S). The compounds 1 – 5 were characterised by X‐ray crystal structure analysis. A di‐substitution reaction occurs on the {Re₆SCl}⁴⁺ cluster core, where the two inner μ₃‐chloro ligands Clⁱ are substituted by X (X = As, P, NH, O, S) and all six terminal chloro ligands Cl^a are exchanged by terminal PPr₃‐ligands.     

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.     

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.