Low-energy fission investigated in reactions of 750 AMeV 238U-ions on 208Pb. II: Isotopic distributions

Projectile fission of 750 AMeV ²³⁸U-ions interacting with a Pb target was studied by means of the spectrometer FRS, GSI-Darmstadt. One of the two fission fragments was detected with a transmission of few percent and identified in mass and charge. Low-energy fission (E^* < 25 MeV) events were selected by their magnetic rigidity. Whereas the production of asymmetric fission events is dominated by the GDR excitation, very asymmetric fission and symmetric fission take place after a GQR or DGDR excitation or after a nuclear interaction. Cross sections of more than 250 isotopes were measured. Isotopic distributions of low-energy fission were reconstructed for elements from Se to Te. The fission modes SI, SII and SL were clearly shown in these distributions and in the mass and TKE distributions. Charge polarization and mass dispersion were deduced for each fission mode. Finally, the characteristics of the low-energy fission process explain the production rates of neutron-rich species. Received: 14 July 1997 / Revised version: 6 October 1997     

Fluctuation kinetics of diffusion-controlled processes: Strong effects due to correlations and fluctuations

We summarize some recent results related to fluctuation-induced kinetics of diffusion-controlled processes. We show that kinetic behavior can be drastically changed due to fluctuation effects, spatial correlations between particles, and anomalous transport properties. In addition, we show that correlation-induced kinetics in some systems can govern the temporal evolution over the entire time domain.     

Recent studies on phosphorus-bridging carbonyl derivatives: organophosphorus analogs of aldehydes and ketones

Reactions of disodium tetracarbonylferrate, Na₂Fe(CO)₄, with sterically hindered dialkylaminodichlorophosphines, R₂NPCl₂ (R₂N=diisopropylamino, dicyclohexylamino, and 2,2, 6, 6-tetramethylpiperidino) in diethyl ether lead to the air-stable phosphorus-bridging carbonyl derivatives (R₂NP)₂COFe₂(CO)₆ as the major products. The phosphorus-bridging carbonyl group in (i-Pr₂NP)₂COFe₂(CO)₆ has been found to undergo the following types of reactions: 1)Reduction, 2)Acylation, 3)Extrusion of the carbonyl group. The mechanisms of the reactions have been considered.This work was presented at the Workshop «The Modern Problems of Heteroorganic Chemistry» held on the ship «Nikolai Bauman» during the period May 8–13, 1993.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1858–1867, November, 1993.     

Ansa macrolides as molecular workbenches for stereoselective additions to achiral (E) olefins

Highly stereocontrolled additions to achiral acyclic (E) olefins are achieved via incorporation into an ansa macrolide with a non-racemic stilbene diol (molecular workbench approach).     

Electron transfer reactions of nickel(III) and nickel(IV) complexes

This review narrates the electron transfer reactions of various nickel(III) and nickel(IV) complexes reported during the period 1981 until today. The reactions have been categorized mainly with respect to the type of nickel complexes. The reactivity of nickel(III) complexes of macrocycles, 2,2′-bipyridyl and 1,10-phenanthroline, peptides and oxime–imine, and of nickel(IV) complexes derived from oxime–imine, oxime and miscellaneous ligands with various organic and inorganic electron donors have been included. Kinetic and mechanistic features associated with such interactions have been duly analyzed. The relevance of Marcus cross-relation equations in the delineation of the electron transfer paths has also been critically discussed.     

Pattern formation in diffusion-limited reactions

The conditions for macroscopic segregation ofA andB in a steady-stateA+B 0 reaction are studied in infinite systems. Segregation occurs in one and two dimensions and is marginal ford=3. We note the dependence of these results on the precise experimental conditions assumed in the theory. We also note the difference between these results and our earlier ones for finite systems where the critical dimension isd=2.     

The elimination of fast variables in complex chemical reactions. III. Mesoscopic level (irreducible case)

The master equation for a complex chemical reaction cannot always be reduced to a simpler master equation, even if there are fast and slow individual reaction steps. Nevertheless the elimination of intermediates can be carried out with the help of the-expansion. This is illustrated with a well-known complex reaction: the dissociation of N₂O₅. It is shown that the intrinsic fluctuations in the N₂O₅ decay are larger than those implied by the master equation suggested by the macroscopic rate law.     

活化/失活反应对原子转移自由基共聚产物微观结构的影响

提出了一个可以处理原子转移自由基共聚及其产物微结构的模型,采用计算机模拟产生了包括活化/失活反应的ATRcP稳态增长反应链,得到了有关链段分布的信息.模拟发现,含有休眠过程的ATRcP产物与常规的自由基的相比组成结构和序列结构完全一致,即活化/失活反应不影响ATRcP产物的微组成与微序列结构.     

Reactivity of stable neopentyl-Pd intermediates in the absence of nucleophile

In the absence of any trapping agent, stable neopentyl-Pd intermediates can terminate a catalytic cycle by undergoing a regioselective C-H activation, leading to various spiro or fused cyclopropane derivatives in a straightforward manner. If the neopentyl-Pd intermediate contains a heteroatom at a suitable position, C-H activation does not occur and stable palladacycles are isolated.