Niederkoordinierte Phosphorverbindungen. 58. Synthese und Reaktivität der 2, 4, 6-Tri-tert-butylphenyl (halogenmethylen)phosphane

The synthesis of the 2,4,6-tri-tert-butylphenyl(halogenmethylene)phosphanes 4a—d from the tri-tert-butylphenylphosphane 1 and trihalogenomethanes 2a—d is described. Tri-tert-butylphenyl(difluoromethylene)phosphane 8a and the analogous (diiodomethylene)-phosphane 8d are obtained by dehalogenation of the chloro(trifluoromethyl)phosphane 7 and dehydrohalogenation of the triiodomethylphosphane 10 . The first different halogeno-substituted (bromochloromethylene)phosphane 8e leads after metallation with lithiumbis (trimethylsilyl)phosphide 13 and elimination of lithiumchloride to the phosphaalkyne 16 . Direct addition of chlorotrimethylsilane to the metallated 8e yields the 2,4,6-tri-tert-butylphenyl(chloro(trimethylsilyl)-methylene)phosphane 17 .     

Photochromism of O-Analogs of Thiathiophthenes

Irradiation of O-analogs of thiathiophthenes yield a photoproduct which reverts thermally to the starting material. Kinetic measurements for this thermal reaction yield E_a values in the range of 10–15 kcal/mol and Δ S* values between ?16 and ?41 eu. Based on NMR. and IR. results the structure of the photoproduct is established. The electronic spectra of the starting material and of the photoproduct are discussed. The experimental results are compared with MO-calculations.     

The n-orbital sequence in 1,3 diazaadamantane

The photoelectron spectra of 1,3-diazaadamantane (1) and 1,3-diaza-6-methyleneadamantane (2) have been measured. An analysis of the spectra based on a ZDO model indicates that the ordering of the n-orbitals in 1 is b₂(n?λσ) above a₁(n₊?λσ). The splitting of b₂ and a₁ in 1 is dominated by the through space interaction. These results are confirmed by semiempirical calculations of the Extended Hückel and MINDO/3 type. An analysis of the PE spectrum of 1,3-diazaadamantanone(6) (5) indicates that in 5 the inductive effect of the CO group is dominant.     

An even magneto-optic effect: Linear polarization of the spectral thermal emission from ferromagnetic iron

The thermal spectral emission from ferromagnetic iron observed at normal incidence and with the magnetization parallel to its surface is partially linearly polarized. Measurements of the new even magneto-optic effect have been performed in the spectral range from 1.8 m to 5 m wave-length.     

Die bestimmung kinetischer parameter endothermer zersetzungsreaktionen unter nicht-isothermen bedingungen

By using the kinetic parameters calculated from non-isothermal measurements according to Freeman and Carroll a computer programm is given, which permits the determination of the more probable reaction mechanism by use of 17 different kinetic equations. The computer programm includes the kinetic equation for chemical reaction, nucleation, phase boundary reaction and diffusion and can easily be extended to other equations. The evaluation of the experimental values by a distinct kinetic equation is quantitatively characterized by means of the correlation coefficient.The kinetic parameters are calculated on the basis of a regression analysis. By dividing the thermogravimetric curve in different reaction intervals a differential calculation is possible.Decomposition of CaCO₃, MgCO₃ and CaSO₄·2H₂O is discussed from the results of the computer calculation. It is seen that the kinetic parameters and the reaction mechanism are not constant during the reaction. Further experiments for a physical interpretation are being carried out.     

Über die oxidative Fluorierung von (CF3)(R) (R = CF3, Cl) und die Kristallstruktur von (CF3)(Cl)F+ AsF6−

Oxidative Fluorination of (CF₃)(R) (R = CF₃, Cl) and the Crystal Structure of (CF₃)(Cl) F⁺ AsF₆^? Oxidative fluorination of (CF₃)(R) (R = CF₃, Cl) with XeF⁺MF₆^? (M = As, Sb) in anhydrous HF results in formation of monofluorsulfonium hexafluorometalates. The salts are characterized by vibrational, NMR, and mass spectra. (CF₃)(Cl)F⁺ AsF₆^? crystallizes in the monoclinic space group P2₁/c with a = 9.955(10) Å, b = 11.050(5) Å, c = 12.733(15) Å, β = 97.77(5)°, and Z = 4.     

Moment multipliers for power series

По определению после довательность {μ _n пр инадлежит классуG _s , если звезда М иттагЛеффлера произвольного степе нного ряда (1) $$\mathop \sum \limits_0^\infty a_n z^n , \mathop {lim sup}\limits_{n \to \infty } \left| {a_n } \right|^{1/n}< \infty $$ , совпадает со звёздам и Миттаг-Леффлера сте пенных рядов $$\mathop \sum \limits_0^\infty \mu _n a_n z^n ,\mathop \sum \limits_0^\infty \mu _n^{ - 1} a_n z^n $$ . В работе установлены следующие утвержден ия Теорема 1.Для произво льной последователь ности ? _n с условиями $$0< \varphi _n< 1,\mathop {lim}\limits_{n \to \infty } \varphi _n = 0,\mathop {lim}\limits_{n \to \infty } \varphi _n^{1/n} = 1$$ существует неубываю щая функция χ(t) такая, ч то моменты \(\mu _n = \int\limits_0^1 {t^n d\chi (t)} \) удовлетворяют условию 0<μ_nn звезда М иттаг-Леффлера любог о ряда (1) совпадает со звездой МиттагЛеффлера степенных рядов . Теорема 2. Для произвол ьной неотрицательно й последовательности {а_n} с условием {a _n } и для любой последов ательности {?_n} для к оторой 0n<1, \(\mathop {\lim }\limits_{n \to \infty } \varepsilon _n = 0\) сущест вуютπ={π _n }∈G _s и последовательнос ть {п_i} такие, что a_nμ_n≦1 (n≧n₀), \(a_{n_i } \mu _{\mu _i } \geqq exp( - \varepsilon _{n_i } )\) (i=1, 2, ...) и при эmom звезда Миттаг-Леффлера ряда (1) совпа дает со звездой Миттаг- Леффлера степенных р ядов .