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1.
On Ordered Perovskites with Cationic Vacancies. XI. Compounds of Type A B B □1/4WVIO6 ? A BIIB □W O24 with AII, BII = Ba, Sr Depending on the ionic radii of the two and three valent cations in the perovskites of type ABB □1/4WVIO6 ?; ABIIB □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.  相似文献   

2.
On Ordered Perovskites with Cationic Vacancies. X. Compounds of Type A B B □1/4MVIO6 ? A BIIB □M O24 with AII, BII = Ba, Sr, Ca and MVI = U, W Perovskites of type Ba8BIIB2III□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 Ba8BIIB□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 ABIIB□W4O24. The higher ordered cells with UVI and WVI are face centered, which has its origin in an ordering of cationic vacancies.  相似文献   

3.
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).  相似文献   

4.
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 fd(WW) = 1.89, fd(WF) = 2.43 and fd(WCl) = 0.93 mdyn/Å.  相似文献   

5.
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 -Th7 (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.  相似文献   

6.
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 Bra 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 Cla 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.  相似文献   

7.
Magnetic interactions in some oxyfluoroferrites of spinel structure with the formula ZnxMe2?xO4?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+]O4?xFx (0 ≤ x ≤ 0,50) spinel, this same substitution leads to a spin canting in the ZnFe[Co2+Fe3+]O4?xFx and ZnFe[Ni2+Fe3+]O4?xFx (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.  相似文献   

8.
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.  相似文献   

9.
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 (νCN), 879–867 (νCS) and 490–482 (δNCS). 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 fd(WW) = 1.61, fd(WI) = 1.23 and fd(WCl) = 1.10 mdyn/Å.  相似文献   

10.
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 Ia 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.  相似文献   

11.
Photoluminescence of Trivalent Rare Earths in Perovskite Stacking Polytypes Ba2La2?x RE MgW2□O12, Ba6Y2?x RE W3□O18, and Sr8SrGd2?xRE W4□O24 Rhombohedral 12 L stacking polytypes Ba2La2?xREMgW2□O12 show with RE3+ = Pr, Sm, Eu, Tb, Dy, Ho, Er, Tm; the 18 L stacking polytypes Ba6Y2?xREW3□O18 and the polymorphic perovskites Sr8SrGd2?xREW4□O24 with RE3+ = Sm, Eu, Dy, Ho, Er visible photoluminescence. The concentration dependence and the influence of the coordination number of the rare earth are reported.  相似文献   

12.
The Crystal Structure of Perovskites A NiIIMVIO6. II. Sr2NiWO6 The results of an X-ray single crystal study of the perovskite Sr[NiIIWVI](6)O6, ordered in the octahedral sites, are given. While Sr[NiIITeVI](6)O6 crystallizes in a monoclinically deformed structure of the perovskite (elpasolite) type, showing a phase transition to a tetragonal lattice at 675 °K, Sr[NiIIWVI](6)O6 is tetragonal already at 298°K (space group: C; a = b = 5.559 Å; c = 7.918 Å; Z = 2). The Ni? O distances found for the tungsten compound are nearly identical with those of the tellurium perovskite. In contradiction to crystal field theory very different values of the ligand field parameter Δ (ca. 25%) are observed for these two compounds however. Obviously this effect is caused by the rather different kind of bonding within the NiO6 polyhedra in the two compounds. On the basis of the structural results the Ni? O-bonding in the two perovskites is discussed in dependence of the next nearest cationic environment.  相似文献   

13.
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).  相似文献   

14.
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.  相似文献   

15.
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.  相似文献   

16.
Reactions of dry THF/MeCN solutions of Ca[Re6SCl(Cla)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 Cla are exchanged by terminal PPr3‐ligands.  相似文献   

17.
On Perovskites A B B WVIO6 Compounds of type ABBWVIO6 can be obtained with AII ? Ba; BI ? Li, Na and BIII ? La, Nd, Sm, Gd, Y, In, Sc just as with AII ? Sr, BI ? Li and BIII ? La, Nd, Sm, Gd, Y, In (all cubic ordered perovskites). For the cubic perovskites Sr2Na0,5La0,5WO6 and Sr2Na0,5Nd0,5WO6 additional superlattice reflections are observed (a ∽ 16.4 Å). The compounds Sr2Na0,5BWO6 crystallize with BIII ? Sm, Gd in a monoclinic and with BIII ? Y, In in a rhombic distorted perovskite lattice. For the perovskites with A = Sr — dependent on ionic radii of the B ions — two different lattice types are present.  相似文献   

18.
Silaheterocycles. III. Synthesis and Reactivity of Di-tbutylneopentylsilaethene, Bu Si?CHCH2But 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 LiBut the first step is the generation of the α-lithio compound BuSi(X)CH(Li)CH2But, 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?CHBut ( 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?CHBut)CH2But ( 13 ) as the main product. BuSi?CHCH2But ( 1 ) probably coordinates to LiBut and reacts to yield BuSiCH?CHBut ( 3 ) and 7 , forms tetrabutyl-dineopentyl-1,3-disilacyclobutane 2 by cyclodimerization and 13 by addition of BuSi(X)CH(Li)CH2But.  相似文献   

19.
K3Au5Pb: Layers of [AuAu3/2] Gold Tetrahedra and [Pb2/2] Lead Chains Silver coloured, brittle single crystals of K3Au5Pb were synthesized by reaction of potassium azide with gold sponge and lead powder at T = 920 K. The structure of the compound (space group Imma, Z = 4, a = 5.646(1) Å, b = 19.500(4) Å, c = 8.412(1) Å) was determined from X-ray single-crystal diffractometry data. The gold lead partial structure consists of layers of [AuAu3/2] tetrahedra and [Pb2/2] zigzag chains with four-bonded lead atoms which are connected to a framework structure via Au–Pb contacts. The potassium atoms occupy channels within the gold lead partial structure.  相似文献   

20.
Kinetic Calculations for the Formation of Chloro-Bromo-Iodo-Osmates(IV) Rate constants of formation and ligand exchange reactions of mixed hexahaloosmates(IV) of the type [OsClxBryI6?x?y]2?, x + y = 2?5, are computable taking into account the relative cis- (f = 1, f = 1.75, f ≈? 6) and trans-effects (f = 1, f = 6, f ≈? 103) of the ligands as well as statistic factors. Using this kinetic data concentration-time diagrams are calculated for reactions including several parallel and consecutive steps. They agree well with the experimentally determined distribution of products in the reaction mixtures. For the preparation of particular mixed ligand complexes the best way of synthesis and maximum yield can be precalculated.  相似文献   

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