Massenspektrometrische Beobachtungen und chemische Transportexperimente mit den Systemen VCl3/Al2Cl6 und VCl2/Al2Cl6

Mass Spectroscopic Observations and Chemical Transport Experiments with the Systems VCl₃/Al₂Cl₆ and VCl₂/Al₂Cl₆ By mass spectrometry the equilibrium VCl_3,s + 0.5 Al₂Cl_6,g ? VAlCl_6,g has been determined: ΔH°(298) = 25.6(±0.5) kcal; ΔS°(298) = 23.0(±3) cal/K, ΔCp (assumed) = ?4 cal/K. This is approximately in agreement with results determined by ligand field spectroscopy by ANUNDSKÅS and ØYE (A. and Ø.). For the dimerization of VCl_3,g values for ΔH and ΔS have been derived. The molecule VAl₂Cl₉ assumed by A. and Ø. could not been observed by mass spectrometry. For the VCl₂/Al₂Cl₆ complex, observed by chemical transport, A. and Ø. give the formula VAl₃Cl₁₁. This molecule could not been observed by mass spectrometry. This suggests a smaller concentration, compared with the results of A. and Ø. Stabilization of VCl_2,s (by metal-nietal-bonds) shifts the reaction to the left, whith explains the lower complex concentration as well as the larger molecular weight of the complex. With chlorides stabilized by stronger metal-metal bonds (MoCl₃, MoCl₂, Nb₃Cl₈) AlCl₃ complexes are not formed in observable concentrations. The chemical transport of VCl₂ with Al₂Cl₆ needs relatively high temperatures (973 → 873 K). In this case the addition of SiCl₄ hinders the attack of the quartz ampoule by Al₂Cl₆. Using a VCl₃ + VCl₂ mixture, VCl₃ is transported by Al₂Cl₆ (673 → 623 K) into the colder region. If afterwords the ampoule is reversed, VCl₃ again moves into the colder region, but the thermal decomposition of VCl₃ at the same time causes that a VCl₂-residue remains in the hot region.     

Das Gleichgewicht CuCl2,f + Al2Cl6,g = CuAl2Cl8,g und die beteiligten Nebenreaktionen

Equilibrium CuCl_2,f + Al₂Cl_6,g = CuAl₂Cl_8,g and the Side Reactions Aim was the measurement of the equilibrium by the flow method. The following observations have been made:

• (a) The solid CuCl₂ phase dissolves 1 mol% CuCl.
• (b) Measurements with CuAl₂Cl₈ as solid phase confirmed this formula for the gas molecule.
• (c) At constant temperature and by variation of P(Al₂C1₆) the expression ΣP(Cu)/P(Al₂Cl₆) passes a flat minimum. This effect is caused by the fact that in the gas phase small concentrations of CuAlCl₅ and CuAl₃Cl₁₁ are present besides the main complex CuAl₂Cl₈. For the formation equilibrium of these side complexes rough thermodynamic data have been given.
• (d) Taking into account the gas molecules Cl₂…Cu₃AlCl₆ (see above) data for the equilibrium (12) have been ascertained, ΔS₁₂°(590) = 8.64 kcal; ΔS₁₂°(590) = 11.24 cal/K.

     

Der chemische Transport von Cu,Ag, Au,Ru, Rh,Pd, Os,Ir, Pt unter Mitwirkung von Gaskomplexen. Al2Cl6, Fe2Cl6 oder Al2J6 als Komplexbildner

The Chemical Transport of Cu, Ag, Au, Ru, Rh, Pd, Os, Ir, Pt in the Presence of Al₂Cl₆, Fe₂Cl₆ or Al₂I₆, Causing Complex Formation Chemical transport experiments show, that the title elements (with exception of Os) in the presence of halide forming agents (HCl, Cl₂ or I₂ resp.) and of complex forming agents (Al₂Cl₆, Fe₂Cl₆ or Al₂I₆ resp.) give gaseous complex compounds with a remarkable stability. This leads to novel possibilities for the chemical transport of the elements and their compounds. The effect of complex formation can be predicted on the basis of qualitative thermodynamic considerations. The corrosion of the wall of the quartz ampoule at temperatures above 600°C by Al₂Cl₆/AlCl₃ is avoidable by the usage of Fe₂Cl₆/FeCl₃ instead of Al₂Cl₆/AlCl₃. Experiments in the system Pd/I₂, Al₂I₆ lead to the formation of crystals of Pd₂Al.     

Die Bildung von CoAl3Cl11 bei größeren Al2Cl6-Drücken

Formation of CoAl₃Cl₁₁ at higher Al₂Cl₆ Pressures The reaction of CoCl_2,f with Al₂Cl_6,g (≈ 3 atm) is investigated considering every component of the gas phase (Al₂Cl₆, AlCl₃, Al₃Cl₉, CoAlCl₅, CoAl₂Cl₈, CoAl₃Cl₁₁) and the deviation from the ideal behaviour. The conclusion is derived that at 600 K from CoCl_2,s and larger pressures of Al₂Cl₆ besides CoAl₂Cl₈ a small amount of CoAl₃Cl₁₁ is formed.     

Die Reaktion von Quarzglas mit Al2Cl6,g und mit Alrf + Al2Cl6,g

Reaction of Quartz Glass with Al₂Cl_6,g and with Al,_f + Al₂Cl_6,g The attack of quartz glass by Al₂Cl_6,g at temperatures ≧ 300°C results in the formation of SiCl_4,g. At low temperature the oxygen appears as gaseous oxide chloride (e. g. Al₄OCl₁₀…); above 300°C crystalline AlOCl is observed, whereas at more elevated temperatures Al₂O₃ is formed. With Al + Al₂Cl₆ (1 atm, 20°C) at 400/350°C thin silicon foils with metallic luster deposit on the quartz wall. Discussion of the experimental evidence leads to the suggestion that the reduction of SiCl₄ — formed initially by attack of the quartz vessel — proceeds by reaction with Al₂Cl_4,g.     

Molecular orbital studies of Al2F6 and Al2Cl6 using a minimal basis set

Ab initio minimal basis LCAO-SCF molecular orbital (MO ) calculations have been carried out on various structures of the AIF₃ and AlCl₃ dimers. A bridged D_2h structure is found to be the most stable of the structures investigated for Al₂F₆. A similar structure was obtained for Al₂Cl₆ in agreement with the experimental evidence.     

Das Gleichgewicht CrCl2,f + Al2Cl6,g  CrAl2Cl8,g und Bemerkungen zum System CrCl3/Al2Cl6,g

Equilibrium CrCl_2,f + Al₂Cl_6,g ? CrAl₂Cl_8,g and Remarks on the System CrCl₃/Al₂Cl_6,g For equation (1) spectralphotometric measurements lead to the data ΔH°(298) = 8.7 kcal; ΔS°(298) = 9.5 cal/K; (ΔCp ? ?1 cal/K). Measurements with CrCl₃/Al₂Cl_6,g confirmed the absorption curve (and therefore the structure) of the complex (CrAl₃Cl₁₂) which we observed earlier. Side reactions (CrCl₃-disproportionation) made the quantitative investigation of the equilibrium impossible.     

Der chemische Transport von CrCl3,f mit Al2Cl6,g über die Gasmolekel CrCl3·3 AlCl3

CrCl₃,_g is chemically transported by means of Al₂Cl_6,g (～1 atm) in a temperature gradient (e. g. 500 → 400°C). Quantitative transport experiments have shown that the reaction goes via the gas molecule CrCl₃ · 3 AlCl₃. Its probable structural formula is CrCl_6/2(AlCl_2/2Cl₂)₃, containing Cr³⁺ in an octahedral and Al³⁺ in a tetrahedral Cl coordination¹).     

Synthesis of Pure Al35Cl3 and Al37Cl3

Chemically and isotopically pure Al³⁵Cl₃ and Al³⁷Cl₃ are synthesized from Al (s) and HCl (g). The yield is quantitative and no measurable decrease in isotopic content from HCl to AlCl₃ takes place.     

Gasförmige BeCl2/AICl3-Komplexe

Gaseous BeCl₂/AlCl₃ complexes During the volatilization of the chlorides of beryllium and aluminium the complex molecules BeAlCl₅, Be₂AlCl₇, BeAl₂Cl₈, Be₂Al₂Cl₁₀, and (in a very small concentration) Be₃Al₂Cl₁₂ have been observed by means of a mass spectrometer. The structure of the compounds is discussed.     

catena‐Poly[bis(trimethylphenylammonium) [hexa‐μ‐chlorido‐dichloridotricuprate(II)]]: an alternating zigzag chain of CuCl4 and Cu2Cl6 complexes

The title compound, {(C₉H₁₄N)₂[Cu₃Cl₈]}_n, consists of parallel chains of alternating quasiplanar Cu₂Cl₆ and planar CuCl₄ complexes separated by trimethylphenylammonium cations. Both inorganic complexes possess inversion symmetry. Pairs of neighboring chloride ions of the CuCl₄ complex each form a symmetric bridge and an asymmetric bridge to Cu₂Cl₆ complexes on either side. The Cu₂Cl₆ complex contains two symmetric chloride bridges between the copper cations with a terminal chloride bound to each five‐coordinated Cu^II ion. The CuCl₄ complex completes its coordination environment by forming two long semicoordinate contacts to the bridging chloride ions of neighboring Cu₂Cl₆ complexes. The use of the bridging rather than the terminal chloride ions to form semicoordinate contacts generates a new zigzag chain structure that differs from the straight chain structures found for other A₂Cu₃Cl₈ compounds. The zigzag chain structure is adopted so as to conform to the shorter repeat distance dictated by stacking of the organic cations.     

SnAl2OCl6, ein quaternäres Oxidchlorid mit kantenverknüpften [Al4O2Cl10]‐Tetrameren und [(SnCl2/2Cl5)2]‐Dimeren

SnAl₂OCl₆, a Quaternary Oxide‐Chloride with Edge‐Sharing [Al₄O₂Cl₁₀] Tetramers and [(SnCl_2/2Cl₅)₂] Dimers Single crystals of SnAl₂OCl₆ were obtained from the educts SnCl₂ and AlCl₃ (obviously containing an oxidic impurity) in silica ampoules with the aid of the Bridgman technique. According to single‐crystal structure analysis, SnAl₂OCl₆ crystallizes with the monoclinic system (P2₁/n, Z = 4, a = 942.3(2), b = 1225.8(2), c = 948.4(3) pm, β = 96.42(2)°). Characteristic structural features are centrosymmetric tetramers [Al₄O₂Cl₁₀] and [(SnCl_2/2Cl₅)₂] dimers which are connected via common edges, finally building up a three‐dimensional structure.     

Synthese und Kristallstrukturen von [Cu4(As4Ph4)2(PRR′2)4], [Cu14(AsPh)6(SCN)2(PEt2Ph)8], [Cu14(AsPh)6Cl2(PRR′2)8], [Cu12(AsPh)6(PPh3)6], [Cu10(AsPh)4Cl2(PMe3)8], [Cu12(AsSiMe3)6(PRR′2)6] und [Cu8(AsSiMe3)4(PtBu3)4] (R,R′ = organische Gruppen)

Syntheses and Crystal Structures of [Cu₄(As₄Ph₄)₂(PRR′₂)₄], [Cu₁₄(AsPh)₆(SCN)₂(PEt₂Ph)₈], [Cu₁₄(AsPh)₆Cl₂(PRR′₂)₈], [Cu₁₂(AsPh)₆(PPh₃)₆], [Cu₁₀(AsPh)₄Cl₂(PMe₃)₈], [Cu₁₂(AsSiMe₃)₆(PRR′₂)₆], and [Cu₈(AsSiMe₃)₄(P^tBu₃)₄] (R, R′ = Organic Groups) Through the reaction of CuSCN with AsPh(SiMe₃)₂ in the presence of tertiary phosphines the compounds [Cu₄(As₄Ph₄)₂(PRR′₂)₄] ( 1 – 3 ) ( 1 : R = R′ = ⁿPr, 2 : R = R′ = Et; 3 : R = Me, R′ = ⁿPr) and [Cu₁₄(AsPh)₆(SCN)₂(PEt₂Ph)₈] ( 4 ) can be synthesised. Using CuCl instead of CuSCN results to the cluster complexes [Cu₁₄(AsPh)₆Cl₂(PRR′₂)₈] ( 5–6 ) ( 5 : R = R′ = Et; 6 : R = Me, R′ = ⁿPr), [Cu₁₂(AsPh)₆(PPh₃)₆] ( 7 ) and [Cu₁₀(AsPh)₄Cl₂(PMe₃)₈] ( 8 ). Through reactions of CuOAc with As(SiMe₃)₃ in the presence of tertiary phosphines the compounds [Cu₁₂(AsSiMe₃)₆(PRR′₂)₆] ( 9 – 11 ) ( 9 : R = R′ = Et; 10 : R = Ph, R′ = Et; 11 : R = Et, R′ = Ph) and [Cu₈(AsSiMe₃)₄(P^tBu₃)₄] ( 12 ) can be obtained. In each case the products were characterised by single‐crystal‐X‐ray‐structure‐analyses. As the main structure element 1 – 3 each have two As₄Ph₄^2–‐chains as ligands. In contrast 4 – 12 contain discrete AsR^2–ligands.     

In Situ Formation of Al(Fe)/Cl Metal Chloride Complexes and Evaluation of Their Catalytic Properties in the Reaction of Ethylene Oligomerization

According to FT-IR and UV spectroscopic data, the interaction of the Al/Fe alloy with tert-butyl chloride results in that AlCl₄^–, Al₂Cl₇^–, and FeCl₂⁺ ion complexes, Fe³⁺ ions, and AlCl₃ molecular form are produced in situ in the reaction medium. Ethylene was oligomerized in n-hexane on metal chloride complexes produced in situ from Al/Fe alloys and tert-butyl chloride.     

Struktur‐Eigenschafts‐Beziehung von Cu5Pb6O3Cl11, einer gut Kupferionen leitenden Verbindung

Structure‐Behaviour‐Relation of Cu₅Pb₆O₃Cl₁₁, a Good Solid State Ionic Conductor for Cu⁺‐Ions A new compound within the group of coin metal lead(II) oxide halides is found and characterized by X‐ray single crystal structure determination in a temperature range from 120 K to 400 K. Cu₅Pb₆O₃Cl₁₁ shows a new crystal type structure with a = 21.098(4) Å, b = 10.233(2) Å, c = 12.224(2) Å, β = 124.08(3)°, Z = 4 and space group C 2/c (No. 15) at 120 K. There are found isolated oxidic chains built of OPb₄ tetrahedra beside columnar areas consisting of CuCl. In this halidic partial structure are a lot of empty and partially occupied Cl₄‐tetrahedra. This structural characteristic seems to be source of a very good conductivity of copper ions, like in microscopic and nanoscaled composites of Al₂O₃ and AgI.     

Die Gasmolekeln Pd2Al2Cl10 und PdAlCl5 als Begleiter von PdAl2Cl8

Gas Molecules Pd₂Al₂Cl₁₀ and PdAlCl₅ as Accompanists of PdAl₂Cl₈ Mass spectrometric observations using a double cell showed that the reaction of gaseous Al₂Cl₆ with solid PdCl₂ besides the known gaseous complex PdAl₂Cl₈ gives PdAlCl₅ and the unexpected complex Pd₂Al₂Cl₁₀. For the equilibrium (with ΔCp? ?1 cal/K) ΔH°(298) = 7.5 kcal/Mol and ΔS°(298) = 5.3 ± 2 cl have been obtained.     

Zur Bildung gasförmiger MCl2-Komplexe. Vergleichende Untersuchung zur Eignung von Al2Cl6, Ga2Cl6, In2Cl6, Fe2Cl6, SiCl4, TiCl4, PCl5, TaCl5 und U2Cl10 als Komplexbildner

Formation of Gaseous MCl₂ Complexes. Comparative Study on the Suitability of Al₂Cl₆, Ga₂Cl₆, In₂Cl₆, Fe₂Cl₆, SiCl₄, TiCl₄, PCl₅, TaCl₅, and U₂Cl₁₀ as Complex Former The thermodynamic data for reactions of the type MCl_2,s + L₂Cl_6,g = ML₂Cl_8,g are – as expected – nearly independent on L(Al, Ga, In, Fe). Transport rates e. g. of CoCl₂ something smaller with L ? Ga may be traced back on uncertainties concerning the Ga₂Cl₆ dissociation, and with L ? Fe they may be traced back on the incorporation of FeCl₂ into MCl_2,s. SiCl₄ and TiCl₄ cause no noticable transport of CoCl₂ or CuCl₂ in a temperature gradient, which leads to a short bond consideration. PCl₅ and TaCl₅ cause the transport of small amounts of CoCl₂. U₂Cl₁₀/UCl₅ are able to transport a remarkable amount of CaCl₂ and CoCl₂, respectively.     

Die gasförmigen Komplexe NiAl2Cl8 und NiAl3Cl11

Gaseous Complexes NiAl₂Cl₈ and NiAl₃Cl₁₁ Spectral photometric measurements of equilibria which are established by reaction of solid NiCl₂ with gaseous Al₂Cl₆ have been made. Results see ?Inhaltsübersicht”?.     

Metallampullen als Mini‐Autoklaven: Synthese und Kristallstrukturen der Ammoniakate [Al(NH3)4Cl2][Al(NH3)2Cl4] und (NH4)2[Al(NH3)4Cl2][Al(NH3)2Cl4]Cl2

Metal Ampoules as Mini‐Autoclaves: Syntheses and Crystal Structures of [Al(NH₃)₄Cl₂][Al(NH₃)₂Cl₄] and (NH₄)₂[Al(NH₃)₄Cl₂][Al(NH₃)₂Cl₄]Cl₂ The salts [Al(NH₃)₄Cl₂]⁺[Al(NH₃)₂Cl₄]^–≡AlCl₃ · 3 NH₃ ( 1 ) and (NH₄⁺)²[Al(NH₃)₄Cl₂]⁺[Al(NH₃)₂Cl₄]^–(Cl^–)₂≡ AlCl₃ · 3 NH₃ · (NH₄)Cl ( 2 ) have been obtained as single crystals during the reactions of aluminum and aluminum trichloride, respectively, with ammonium chloride in sealed Monel metal containers. The crystal structure of 1 was determined again [triclinic, P‐1; a = 574.16(10); b = 655.67(12); c = 954.80(16) pm; α = 86.41(2); β = 87.16(2); γ = 84.89(2)°], that of 2 for the first time [monoclinic, I2/m; a = 657.74(12); b = 1103.01(14); c = 1358.1(3) pm; β = 103.24(2)°].     

Über ternäre Oxocuprate. X. Zur Kenntnis von Ba2Cu3O4Cl2

About Ternary Oxocuprates. X. On Ba₂Cu₃O₄Cl₂ The preparation of Ba₂Cu₃O₄Cl₂ and results by single crystal X-ray methods are described (a = 5.517, c = 13.808 Å; Space group D–I4/mmm). A so far unknown arrangement of square coordinated Cu²⁺ was detected. The Cu²⁺/O^2?-squares are partly completed to a distorted octahedral coordination by two Cl^?.