Samarium(II)-mediated reactions of gamma,delta-unsaturated ketones. Cyclization and fragmentation processes

[reaction: see text] On treatment with samarium(II) iodide, gamma,delta-unsaturated ketones undergo very different processes depending upon the nature of the reaction conditions. Employing samarium(II) iodide and MeOH, functionalized syn-cyclopentanol products are obtained stereoselectively. Mechanistic studies suggest that this cyclization occurs via a sequential reduction/intramolecular aldol reaction. With samarium(II) iodide and HMPA, products of a 4-exo-trig cyclization and of an interesting fragmentation reaction are observed.     

1,2-Dialkoxyacenaphthylenes and 2,3,11,12-bis-(1,2-acenaphtho)-[18]crown-6

A general synthesis of 1,2-dialkoxyacenaphthylenes by dehydrogenation of the corresponding acenaphthene derivatives with high potential quinones is described. The new crown ether, 2,3,11,12-bis(1,2-acenaphtho)-[18]crown-6, 1, is obtained by this route. The surprisingly poor complexing ability of 1 is ascribed to electronic and geometrical effects of the acenaphthylene rings as shown by spectroscopic and voltammetric data and the crystal structure of the free ligand 1.     

Dipole-bound anions of highly polar molecules: ethylene carbonate and vinylene carbonate

Results of experimental and theoretical studies of dipole-bound negative ions of the highly polar molecules ethylene carbonate (EC, C3H4O3, mu=5.35 D) and vinylene carbonate (VC, C3H2O3, mu=4.55 D) are presented. These negative ions are prepared in Rydberg electron transfer (RET) reactions in which rubidium (Rb) atoms, excited to ns or nd Rydberg states, collide with EC or VC molecules to produce EC- or VC- ions. In both cases ions are produced only when the Rb atoms are excited to states described by a relatively narrow range of effective principal quantum numbers, n*; the greatest yields of EC- and VC- are obtained for n*(max)=9.0+/-0.5 and 11.6+/-0.5, respectively. Charge transfer from low-lying Rydberg states of Rb is characteristic of a large excess electron binding energy (Eb) of the neutral parent; employing the previously derived empirical relationship Eb=23/n*(max)(2.8) eV, the electron binding energies are estimated to be 49+/-8 meV for EC and 24+/-3 meV for VC. Electron photodetachment studies of EC- show that the excess electron is bound by 49+/-5 meV, in excellent agreement with the RET results, lending credibility to the empirical relationship between Eb and n*(max). Vertical electron affinities for EC and VC are computed employing aug-cc-pVDZ atom-centered basis sets supplemented with a (5s5p) set of diffuse Gaussian primitives to support the dipole-bound electron; at the CCSD(T) level of theory the computed electron affinities are 40.9 and 20.1 meV for EC and VC, respectively.     

An integral representation for decomposable measures of measurable functions

Summary We start with a measurem on a measurable space (,A), decomposable with respect to an Archimedeant-conorm on a real interval [0,M], which generalizes an additive measure. Using the integral introduced by the second author, a Radon-Nikodym type theorem, needed in what follows, is given.The integral naturally leads to a -decomposable measurem on the space of all measurable functions from to [0, 1]. The main result of the present paper is the converse of this, namely that, under natural conditions, any -decomposable measurem on can be represented as an integral of a certain Markov-kernelK. We extend this representation to measures on which have values in a set of distribution functions.These results generalize the work done by the first author in the case of additive measures.     

Initial data truncation for multivariate output of discrete-event simulations using the Kalman filter

Data truncation is a commonly accepted method of dealing with initialization bias in discrete-event simulation. An algorithm for determining the appropriate initial-data truncation point for multivariate output is proposed. The technique entails averaging across independent replications and estimating a steady-state output model in a state-space framework. A Bayesian technique called Multiple Model Adaptive Estimation (MMAE) is applied to compute a time varying estimate of the output's steady-state mean vector. This MMAE implementation features the use, in paralle, of a bank of Kalman filters. Each filter is constructed under a different assumption concerning the output's steady-state mean vector. One of the filters assumes that the steady-state mean vector is accurately reflected by an estimate, called the assumed steady-state mean vector, taken from the last half of the simulation data. As the filters process the output through the effective transient, this particular filter becomes more likely (in a Bayesian sense) to be the best filter to represent the data and the MMAE mean estimator is influenced increasingly towards the assumed steady-state mean vector. The estimated truncation point is selected when a norm of the MMAE mean vector estimate is within a small tolerance of the assumed steady-state mean vector. A Monte Carlo analysis using data from simulations of open and closed queueing models is used to evaluate the technique. The evaluation criteria include the ability to construct accurate and reliable confidence regions for the mean response vector based on the truncated sequences.     

CEMS and DCEMS investigations of Al-implanted iron

-Fe surfaces were implanted with a nominal dose of 5×10¹⁷ Al ions/cm² at 50 keV and a current density of about 3.7 A/cm². Samples of different shapes and thicknesses have been used in order to test the influence of heat flow from specimen to target holder during implantation. Integral and energy differential (depth-selective)⁵⁷Fe conversion electron Mössbauer spectroscopy (CEMS and DCEMS) were employed. The spectra indicated a magnetic phase characterised by a broad hyperfine field distributionP(B _hf), a non-magnetic phase, and -Fe. The relative intensity of the non-magnetic phase was enhanced if the thermal contact during implantation became worse. An energy dependence of DCEM spectra in the L-electron range was observed. Model calculations using L-electron weight functions and experimental concentration profiles obtained by secondary neutral mass spectroscopy (SNMS) yielded fair agreement between calculated and experimental phase signals. The results demonstrate that the non-magnetic Fe-Al alloy phase with high Al concentration is located closer to the surface than the magnetic alloy phase, which extends to much larger depth than expected.