Bildung siliciumorganischer Verbindungen. 97. Über den Einfluß der Si-Substituenten (Me,Cl) auf Bildung und Reaktion von Yliden

Formation of Organosilicon Compounds. 97. About the Influence of the Si-Substituents (Me, Cl) upon the Formation and the Reactions of Ylides 1,3-disilapropanes with different grade of chlorination or methylation at the silicon atoms and containing a CCl₂ group cleave the Si? P bond of Me₃SiPMe₂. By subsequent rearrangement ylides with ? PMe₂Cl group are formed. The reactivity of the CCl₂ group depends on the grade of Si-chlorination resp. Si-methylation. Si-methylation decreases the reactivity of the CCl₂ group. The reaction of 1,3-disilapropanes and Me₃SiPMe₂ (molar ratio 1:1) runs in a sequence shown in “Inhaltsübersicht”. Ylid C is able either to react with the initial compound A forming B, or in competition decomposes forming D. Reacting Si-perchlorinated carbosilanes, the decomposition forming D is not to be observed. In Si-methylated ylides like (Me₃Si)₂C?PMe₂? PMe₂ and (Me₃Si)₂C?PMe₂? P(Me)SiMe₃ the ylid carbon atom is able to abstract a proton of the P? CH₃ group resp. P? H groups of the trivalent phosphorus forming (Me₃Si)₂C(H)PMe₂. The rearrangement is proved by deuterated derivatives. The different behaviour is due to the increased basicity of the ylid-C atom in Si-methylated phosphorus ylides. Quite the same behaviour show the phosphorus ylides of 1,3,5-trisilacyclohexane.     

Einfluß der Chelatbildner dppe und dppp auf die Bildung und die Eigenschaften der Pt-Komplexe des tBu2P–P

Coordination Chemistry of P-rich Phosphanes and Silylphosphanes. XV. Influence of the Chelate Compounds dppe and dppp on Formation and Properties of the Pt Complexes of ^tBu₂P–P The chelating ligands dppe and dppp replace the PPh₃ groups in [η²-{^tBu₂P–P}Pt(PPh₃)₂] 1 yielding [η²-{^tBu₂P–P}Pt(dppe)] 2 and [η²-{^tBu₂P–P}Pt(dppp)] 8 . However, they don't replace the phosphinophosphinidene ligand ^tBu₂P–P. dppm does not react at all with 1 . [η²-{H₂C=CH₂}Pt(dppe)] 3 yields in the presence of ^tBu₂P–P=P(Me)^tBu₂ 4 exclusively Pt(dppe)₂ 5 and elemental Pt; no 2 could be detected. Similarly, [η²-{H₂C=CH₂}Pt(dppp)] 7 reacts with 4 to give mainly Pt(dppp)₂ 9 and Pt; [η²-{tBu₂PP}Pt(PPh₃)₂] 8 is present only as a minor product. [η²-{^tBu₂P–P}Pt(dppe)] 2 crystallizes in the monoclinic space group P2₁/c (no. 14) with a = 1834.40(10) pm, b = 1679.70(10) pm, c = 1125.79(6) pm, β = 103.963(5)°.     

Über den Einfluß von Temperatur und Fremdionen auf Eigenschaften und Bau der Natriumwasserglaslösungen

The Influence of Temperature and Impurities Addition on the Properties and the Constitution of Sodium Water Glass Solutions Sodium water glass (NaWG-)solutions of constant composition (SiO₂/Na₂O = 3,3; C_SiO2 = 6,2 M) and different concentration of impurities (Fe, Al, Ti, Cu, chloride, sulfate) were investigated in dependence on temperature by means of the dye absorption method, ¹H- and ²³Na-NMR spectroscopy. It is shown, that the differences in the dye absorption spectra of normalized technical NaWG-solutions, mainly depend on the Fe-concentration in the solutions and their thermal history. From the results follow a crosslinking of polymeric silicate species by Fe? O? Si bonds and/or hydrogen bridges and a fully or partially degradation of these bonds at higher temperatures (150°C).     

Über den Einfluß von Kristallkeimen auf die Bildung von Silicaten der Zusammensetzung 3 CaO · 2 SiO2

On the Influence of Seed Crystals on the Formation of Calcium Silicates with the Composition 3 CaO · 2 SiO₂ The formation of the calcium silicates kilchoanite and rankinite of the composition 3 CaO · 2 SiO₂ is facilitated and enabled, respectively, in the presence of appropriate seed crystals. Kilchoanite (Ca₆[(SiO₄)(Si₃O₁₀)]) is formed from mixtures of CaO and SiO₂ in the autoclave at 200°C and from C? S? H (di, poly) under normal atmosphere at 700°C by seeding for example with kilchoanite, aluminium compounds, γ-Ca₂SiO₄. Rankinite (Ca₃Si₂O₇) can be synthesized under the same conditions, when rankinite itself is applied as seed crystal.     

Über Bildung und Reaktionen der CH2Li‐Derivate von tBu2P–P=P(CH3)tBu2 und (Me3Si)tBuP–P=P(CH3)tBu2

Formation and Reactions of the CH₂Li‐Derivatives of ^tBu₂P–P=P(CH₃)^tBu₂ and (Me₃Si)^tBuP–P=P(CH₃)^tBu₂ With ⁿBuLi, (Me₃Si)^tBuP–P=P(CH₃)^tBu₂ ( 1 ) and ^tBu₂P–P=P(CH₃)^tBu₂ ( 2 ) yield (Me₃Si)^tBuP–P=P(CH₂Li)^tBu₂ ( 3 ) and ^tBu₂P–P=P(CH₂Li)^tBu₂ ( 4 ), wich react with Me₃SiCl to give (Me₃Si)^tBuP–P=P(CH₂–SiMe₃)^tBu₂ ( 5 ) and ^tBu₂P–P=P(CH₂–SiMe₃)^tBu₂ ( 6 ), respectively. With ^tBu₂P–P(SiMe₃)–P^tBuCl ( 7 ), compound 3 forms 5 as well as the cyclic products [H₂C–P(^tBu)₂=P–P(^tBu)–P^tBu] ( 8 ) and [H₂C–P(^tBu)₂=P–P(P^tBu₂)–P(^tBu)] ( 9 ). Also 3 forms 8 with ^tBuPCl₂. The cleavage of the Me₃Si–P‐bond in 1 by means of C₂Cl₆ or N‐bromo‐succinimide yields (Cl)^tBuP–P=P(CH₃)^tBu₂ ( 10 ) or (Br)^tBuP–P=P(CH₃)^tBu₂ ( 11 ), resp. With LiP(SiMe₃)₂, 10 forms (Me₃Si)₂P–P(^tBu)–P=P(CH₃)^tBu₂ ( 12 ), and Et₂P–P(^tBu)–P=P(CH₃)^tBu₂ ( 13 ) with LiPEt₂. All compounds are characterized by ³¹P NMR Data and mass spectra; the ylide 5 and the THF adduct of 4 additionally by X‐ray structure analyses.     

Bildung siliciumorganischer Verbindungen. 96. Bildung und Struktur von P-Yliden des 1,3,5-Trisilacyclohexans (Einfluß der Substituenten)

Formation of Organosilicon Compounds. 96. Preparation and Structure of P-Ylides of the 1,3,5-Trisilahexanes (Influence of the Substituents) The influence of the substituents at the silicon atoms on formation and structure of ylides of 1,3,5-trisilacyclohexanesis investigated. The reactions of 1 , 2 , 3 with Me₃Si? PMe₂ lead via cleavage of the Si? P bond and subsequent rearrangement to the ylides 4 , 5 and 6 . The x-ray structure determination reveals, that the atoms of the ylid part of 4 are in a plane with the shortened bond distances d(C? P) = 168.6 pm and d(Si? C) = 180.1 pm, whereas the other endocyclic Si? C distances remain nearly unaffected by the ylid formation. Only the endocyclic bond angles C? Si? C of the Si atoms of the ylid are enlarged (116°). In the molecule 6 d(C? P) = 164.6 pm is much shorter, but d(P? Br) = 236.6 pm is enlarged. This enlargement is coupled with a deviation of 17 pm for the ylidic C atom from the ylid plane. Distances and angles are normal in the methylated trisilnhexane. The ring in 6 has boat conformation, in 4 a flat chair conformation.     

Bildung siliciumorganischer Verbindungen. 112. Über den Einfluß der Reaktionsbedingungen auf die Umsetzung von (Cl3Si)2CCl2 mit Silicium. Die Struktur von 2,2,3,3,5,5,6,6-Octachlor-1,4-bis(trichlorsilyl)-2,3,5,6-tetrasilabicyclo[2.1.1]hexan und 1,1,3,4,6,6-Hexakis(trichlorsilyl)hexatetraen

Formation of Organosilicon Compounds. 112. The Influence of Reaction Conditions on the Reaction of (Cl₃Si)₂CCl₂ with Silicon. The Structures of 2,2,3,3,5,5,6,6-Octachloro-1,4-bis(trichlorosilyl)-2,3,5,6-tetrasilabicyclo[2.1.1]-hexane and 1,1,3,4,6,6-Hexakis(trichlorosilyl)hexatetraene While reactions of (Cl₃Si)₂CCl₂ 1 with Si(Cu) in a fluid bed at 320°C exclusively yield products by silylation of the CCl₂ group in 1 does the reaction in a stirred bed preferrably give rize to chlorosilanes containing C? C double and triple bonds. Compounds 5, 6, 7, 8 and 9 in Tab. 1 belong to the first group, whereas 3 and 4 belong to the second one. The reaction of 1 with elemental copper under dehalogenation at carbon produces 3, 4 and 11 . In the reaction of 1 with CaSi₂ no additional Si? C bonds are formed, exclusively chlorosilanes with multiple C? C bonds as 3, 4 and 10 were found besides of SiCl₄. The bicyclo[2.1.1]hexane 6 (Tab. 1) crystallizes monoclinically in the space group C2/c (no. 15) with a = 1557.8, b = 857.4, c = 1727.3 pm, β = 104.34° und Z = 4 molecules per unit cell; the hexatetraene 10 (Tab. 1) crystallizes monoclinically in the space group C2/m (no. 12) with a = 1189.6, b = 1433.8, c = 983.5 pm, β = 98.75° pm, and Z = 2 molecules per unit cell. The skeleton of 6 is a system of high bond stress with 2-C₂ symmetry. The strongly folded (138.8°) four-membered ring (sum of angles = 344.2°) and the presence of both a Si? Si bond length of 238.2 pm and a Si? Si non-bonding distance of 255.1 pm are remarkable aspects of this feature. The mean bond lengths in the bicyclic compound were found to be d(Si? C) = 190.9 pm and d(Si? C) = 185.1 pm for exo- and endocyclic bonds, respectively. The skeleton of 10 is of the symmetry 2/m-C_2h. The six-membered chain is plane. The central C? C single bond length and the mean distance of the cumulated double bonds are 148.6 pm and 130.5 pm, respectively.     

Zum Einfluß der Substituenten R = Ph,NEt2, iPr und tBu in Triphosphanen, (R2P)2P?SiMe3, und Phosphiden,Li(THF)2[(R2P)2P], auf die Bildung und Eigenschaften von Phosphinophosphiniden-Phosphoranen

Concerning the Influence of the Substituents R = Ph, NEt₂, ⁱPr, and ^tBu in Triphosphanes (R₂P)₂P? SiMe₃ and Phosphides Li(THF)₂[(R₂P)₂P] on the Formation and Properties of Phosphino-phosphinidene-phosphoranes The triphosphanes X₂P? P(SiMe₃)? PY₂ 5, 7, 9, 11, 13 and the derived phosphides Li(THF)₂[X₂P? P? PY₂] 6, 8, 10, 12, 14 were synthesized: 5 and 6 with X₂ = ⁱPr₂ and Y₂ = ^tBu₂, 7 and 8 with X₂ = Y₂ = Ph^tBu, 9 and 10 with X₂ = ^tBu₂ and Y₂ = Ph₂, 11 and 12 with X₂ = Y₂ = Ph₂, and 13 and 14 with X₂ = ^tBu₂ and Y₂ = (NEt₂)₂. The silylated triphosphanes at ?70°C in toluene with CBr₄ may yield X₂P? P?P(Br)Y₂ and X₂P? P(Br)? PY₂, and the lithiated phosphides with MeCl may yield X₂P? P?P(Me)Y₂ and X₂P? P(Me)? PY₂ depending on X and Y. The bromiated product of 5 (X₂ = ⁱPr₂, Y₂ = ^tBu₂) is the ylide ⁱPr₂P? P?P(Br)^tBu₂, and the methylated derivatives of 6 are both ⁱPr₂P? P?P(Me)^tBu₂, ^tBu₂P? P?P(Me)ⁱPr and the methylated triphosphane. Ph₂P? P?P(Br)^tBu₂ as well as the brominated triphosphane are obtained from 9 (X₂ = ^tBu₂, Y₂ = Ph₂), and similarly Ph₂P? P?P(Me)^tBu₂ and the methylated triphosphane from 10 . Compound 14 (X₂ = ^tBu₂, Y₂ = (NEt₂)₂ gives rise to the brominated ylide ^tBu₂)P? P?P(Br) · (NEt₂)₂ and to the brominated triphosphane, and on methylation to ^tBu₂P? P?P(Me)(NEt₂)₂ and to ^tBu₂P? P(Me)? P · (NEt₂)₂ (main product). The Br substituted derivatives decompose already on warming to ?30°C, while the methylated compounds are stable up to 20°C.     

Über den Einfluß von Substitution auf die Kristallstruktur von SrNi2P2

About the Effect of Substitution on the Crystal Structure of SrNi₂P₂ With several series of mixed crystals the effect of substitution on the crystal structure of SrNi₂P₂ (polymorphic, the structures are variants of the ThCr₂Si₂ type) is investigated by X-ray methods. In the compound Ni completely can be substituted by Co and Cu respectively and also P by As; in Sr_1–xCa_xNi₂P₂ there is a gap of the miscibility between 0.3 ≤ x ≤ 0.6. A low substitution of the several elements more than proportionally changes the structure parameters. In this range the mixed crystals with Ca, Cu, and As, respectively, undergo first order phase transitions with significant changes of the bond distances, which will be interpreted by the results of band structure calculations.     

Über den Mechanismus der Bildung von Chrom(IV)-oxid aus Chromylchlorid

On the Mechanism of the Formations of Chromium(IV)oxide from Chromyl Chloride The decomposition of chromyl chloride in the temperature range from 380 to 400°C leads with increasing oxygen pressure to chromium oxides containing up to nearly 90% of CrO₂. The interaction with the chlorine prevents a quantitative formation of CrO₂. Up to 315°C during the decomposition of chromyl chloride chromium oxides of higher valencies are formed separating chlorine and taking up oxygen simultaneously. By working in flowing oxygen it could be proved that the decomposition goes at lower temperatures via the nondetectable CrO₃. By heating gradually and by removing the chlorine as far as possible stoichiometric CrO₂ at oxygen pressures above 60 atm could be obtained.     

Über den Einfluss der pK-Werte von Anilinen auf die Bildung und Folgereaktionen von substituierten Butadienen aus Cumalinsäure-methylester

The Influence of Aniline pK Values on the Formation and Reactivity of Substituted Butadienes from Methyl Coumalate The product of the reaction between 2 equiv. of methyl coumalate ( 1 ) and 1 equiv. of a substituted aromatic amine depends on the pK value of the latter. Aromatic amines with pK values between 1.05 and 2.8 produce bicyclic lactones 4 , whereas those with higher pK values also give 2-azabicyclo[3.3.1]nona-3,7-diene-9-carboxylic acids 9 . The latter, products of the intramolecular Diels-Alder reaction 8 → 9 , may in certain cases even prevail.     

Über den thermischen Abbau einiger Alkalimetall- und Ammoniumhalogenoaurate(III) und die Kristallstruktur der Zersetzungsprodukte Rb2Au2Br6, Rb3Au3Cl8 und Au(NH3)Cl3

Thermal Decomposition of Some Alkali Metal and Ammonium Halogenoaurates(III), and the Crystal Structure of the Decomposition Products, Rb₂Au₂Br₆, Rb₃Au₃Cl₈, and Au(NH₃)Cl₃ The thermal decomposition of the salts MAuX₄ and M₂Au₂I₆, with M = K, NH₄, Rb; and X = Cl, Br; has been investigated. With the exception of NH₄AuCl₄ and KAuCl₄, all decompose with loss of halogen to the mixed valence compound M₃Au₃X₈, sometimes via the intermediate M₂Au₂X₆. Tetraiodoaurates are not stable at room temperature. In the decomposition of NH₄AuCl₄, HCl, and Au(NH₃)Cl₃ are formed. KAuCl₄ decomposes directly into Au und KCl. The crystal lattices of the salts Rb₂Au₂Br₆ and Rb₃Au₃Cl₈ are monoclinic and built up from Rb⁺. AuX₂^?, and AuX₄^? ions. There exists a close structural relationship between Rb₂Au₂Br₆, Cs₂Au₂Cl₆, and the perovskite structure. Rb₂Au₂I₆ is isotypic with Rb₂Au₂Br₆. The Rb₃Au₃Cl₈ structure type is also observed for the M₃Au₃X₈ salts with M = NH₄, K, Rb; and X = Br, I. In the structure of Au(NH₃)Cl₃ there are discrete molecules in which Au(III) is surrounded by 3 Cl and 1 N atoms in square coplanar coordination. The infrared spectra of these compounds are discussed.     

Der Transport von VO2 mit Cl2 und HCl + Cl2 und der Einfluß des O2-Bodenkörpergleichgewichtsdruckes auf den Transport

The Chemical Transport of VO₂ with Cl₂ and HCl + Cl₂ and the Influence of the O₂-Coexistence Equilibrium Pressure on the Transport Behaviour The transport behaviour of VO₂ with Cl₂, HCl, and Cl₂ was calculated and compared with the experimental results. VO₂ with the upper phase boundary transports with HCl and HCl + Cl₂ from the colder to the hotter zone, VO₂ of the lower phase boundary does not transport with HCl. The composition of the deposited VO₂ is near the upper boundary oxygen richer than in the start space. VO₂ does not transport with Cl₂.     

Zum Einfluß der PR3‐Liganden auf Bildung und Eigenschaften der Phosphinophosphiniden‐Komplexe [{η2‐tBu2P–P}Pt(PR3)2] und [{η2‐tBu2P1–P2}Pt(P3R3)(P4R′3)]

Coordination Chemistry of P‐rich Phosphanes and Silylphosphanes XXI The Influence of the PR₃ Ligands on Formation and Properties of the Phosphinophosphinidene Complexes [{η²‐^tBu₂P–P}Pt(PR₃)₂] and [{η²‐^tBu₂P¹–P²}Pt(P³R₃)(P⁴R′₃)] (R₃P)₂PtCl₂ and C₂H₄ yield the compounds [{η²‐C₂H₄}Pt(PR₃)₂] (PR₃ = PMe₃, PEt₃, PPhEt₂, PPh₂Et, PPh₂Me, PPh₂ⁱPr, PPh₂^tBu and P(p‐Tol)₃); which react with ^tBu₂P–P=PMe^tBu₂ to give the phosphinophosphinidene complexes [{η²‐^tBu₂P–P}Pt(PMe₃)₂], [{η²‐^tBu₂P–P}Pt(PEt₃)₂], [{η²‐^tBu₂P–P}Pt(PPhEt₂)₂], [{η²‐^tBu₂P–P}Pt(PPh₂Et)₂], [{η²‐^tBu₂P–P}Pt(PPh₂Me)₂], [{η²‐^tBu₂P–P}Pt(PPh₂ⁱPr], [{η²‐^tBu₂P–P}Pt(PPh₂^tBu)₂] and [{η²‐^tBu₂P–P}Pt(P(p‐Tol)₃)₂]. [{η²‐^tBu₂P–P}Pt(PPh₃)₂] reacts with PMe₃ and PEt₃ as well as with ^tBu₂PMe, PⁱPr₃ and P(c‐Hex)₃ by substituting one PPh₃ ligand to give [{η²‐^tBu₂P¹–P²}Pt(P³Me₃)(P⁴Ph₃)], [{η²‐^tBu₂P¹–P²}Pt(P³Ph₃)(P⁴Me₃)], [{η²‐^tBu₂P¹–P²}Pt(P³Et₃)(P⁴Ph₃)], [{η²‐^tBu₂P¹–P²}Pt(P³Me^tBu₂)(P⁴Ph₃)], [{η²‐^tBu₂P¹–P²}Pt(P³ⁱPr₃)(P⁴Ph₃)] and [{η²‐^tBu₂P¹–P²}Pt(P³(c‐Hex)₃)(P⁴Ph₃)]. With ^tBu₂PMe, [{η²‐^tBu₂P–P}Pt(P(p‐Tol)₃)₂] forms [{η²‐^tBu₂P¹–P²}Pt(P³Me^tBu₂)(P⁴(p‐Tol)₃)]. The NMR data of the compounds are given and discussed with respect to the influence of the PR₃ ligands.     

Der Einfluß von Phosphoryl‐Substituenten auf die Eigenschaften P‐substituierter 2‐Methylimidazolium‐Ionen und 2‐Methylenimidazoline [1]

The Influence of Phosphoryl Substituents on the Properties of P‐Substituted 2‐Methylimidazolium Ions and 2‐Methyleneimidazolines [1] The imidazolines ImCHP(E)Ph₂ [ 6 , E = S ( a ), Se ( b )] are obtained from ImCHPPh₂ ( 4 ) and sulfur or selenium. HBF₄ reaction yields the corresponding imidazolium salts [ImCH₂P(E)Ph₂][BF₄] [ 5 , E = S ( a ), Se ( b )]. 1, 3, 4, 5‐Tetramethyl‐2‐methylenimidazoline ( 1 , ImCH₂) reacts with Ph₂P(O)Cl to give the corresponding phosphane salt [ImCH₂P(O)Ph₂]Cl ( 7 ) from which the vinyl compound ImCHP(O)Ph₂ ( 8 ) is formed through deprotonation. 8 reacts with excess HBF₄ to give the phosphine oxide BF₃ adduct [ImCH₂P(O)Ph₂ · BF₃][BF₄] ( 9 ). The crystal structures of 5a , 5b , 6b , 7 · CH₂Cl₂ and 9 · H₂O as well as preliminary data of 8 are reported and discussed on comparison with the phosphanes [ImCH₂PPh₂][BF₄] ( 3b ) and ImCHPPh₂ ( 4 ). From structural data, π‐electron delocalisation is concluded for 6b and 8 .     

Bildung und Eigenschaften von Li2P7R (R = Si(CH3)3, CH3, C(CH3)3)

Formation and Properties of Li₂P₇R (R = Si(CH₃)₃, CH₃, C(CH₃)₃) The reaction of P₇(Sime₃)₃ with Li₃P₇ in the molar ratio of 2:1 yields LiP₇(Sime₃)₂, and in the molar ratio of 1:2 Li₂P₇Sime₃ is formed. Li₂P₇me and Li₂P₇Cme₃ (me = CH₃) are obtained by reaction of white phosphorus with Lime, or LiCme₃, respectively [2]. The compounds Li₂P₇R (R = Sime₃, Cme₃, me) show typical valence tautomerism, as established by ³¹P-n.m.r. spectroscopy at various temperatures. Also LiP(Sime₃)₂ transforms P₇(Sime₃)₃ to yield Li₂P₇Sime₃ but in this reaction considerable cleavage of P? P bonds occurs, too.     

Über Glasbildung und Eigenschaften von Chalkogenidsystemen. VII. Anwendung der Theorie des freien Volumens auf Gläser und Schmelzen im System Germanium-Selen

Application of the Free Volume Theory to Glasses and Melts in the System Germanium–Selenium The temperature dependence on the molar volume of glasses and melts was measured for the compositions: Ge₅Se₇, Ge₂Se₃, Ge₃Se₇, GeSe₃, GeSe₅. Values of the free volume were calculated. Correlating this values according to free volume theory with data from the literature concerning the viscosity of the melts allows the estimation of the minimum required volume of the voids. Se is found as the unit of viscous flow for GeSe₂?Se-melts. The mechanism is discussed.