Komplexkatalyse: XXV. 31P-NMR-spektroskopische charakterisierung der anti- und syn-struktur von C3-substituierten η3-allylbis(triarylphosphit)-nickel(II)-hexafluorophosphat-komplexen und der mechanismus der durch [C3H5Ni(P(OPh)3)2]PF6 katalysierten 1,4-trans-polymerisation des butadiens

The reaction of the η₃-allylbis(triarylphosphite)nickel(II) complexes with butadiene under chain propagation to give the polybutadienyl complex, [3-RC₃H₄Ni(P(OAr)₃)₂]PF₆, was monitored by ³¹P NMR spectroscopy. In the case of the triphenylphosphite complex both the anti- and the syn-configuration could be identified by means of their different AB spectra. The anti-syn isomerization, the higher reactivity of the thermodynamically more stable syn-form, and the formation of the anti-structure as a result of each individual butadiene insertion step was also proved. From these observations an experimentally well-grounded mechanism of the trans regulation with the anti-syn isomerization as the rate-determining step could be derived for the first time.     

The angular dependence of flux,mean energy and speed ratio for D2 molecules desorbing from a Ni(111) surface

Experimental data are presented for the angular dependence of the relative flux, the mean energy and the speed ratio of deuterium molecules desorbing from a Ni(111) crystal surface at a surface temperature of T_s = 1143 K and at sulphur coverages ranging between 30% and less than 2% of a monolayer.The angular flux distribution is sharply peaked in the forward direction (cos^dθwith 3 ? d ? 5) and the mean energy 〈E〉 of the desorbate depends strongly on the desorption angle θ. For normal desorption $\text{(θ = 0°)}\text{〈E〉}\text{2k}$ is about 700 K higher than T_s and for glancing angles (θ = 80°) it decreases to about 400 K below T_s The results obtained on sulphur free and sulphur covered Ni(111) surfaces are compared with our former data on polycrystalline nickel. The main differences in the kinetic features can be ascribed to the surface roughness. Accordingly, the angular distributions of flux, mean energy, and speed ratio, which deviate strongly from the Knudson and Maxwellian law, do not seem to depend considerably on sulphur coverage and surface structure. A qualitative explanation for these deviations is presented using the principle of detailed balancing.     

Stability and equilibrium states

For an infinite dynamical quantum system idealized as aC*-algebra acted upon by time-translations automorphisms in an asymptotically abelian way, we propose to characterize equilibrium states by the three properties of stationarity, stability for local perturbations of the dynamics, and relative purity. We show that a state with these properties either gives rise to a one-sided energy spectrum or is a KMS- (i.e. essentially a limit Gibbs-) state.