Synthesis and redox behaviour of the chalcogenocarbonyl dianions [(E)C(PPh(2)S)(2)](2-): formation and structures of chalcogen-chalcogen bonded dimers and a novel selone

The lithium salts of the chalcogenocarbonyl dianions [(E)C(PPh₂S)₂]^2? (E=S ( 4 b ), Se ( 4 c )) were produced through the reactions between Li₂[C(PPh₂S)₂] and elemental chalcogens in the presence of tetramethylethylenediamine (TMEDA). The solid‐state structure of {[Li(TMEDA)]₂[(Se)C(PPh₂S)₂]}—[{Li(TMEDA)}₂ 4 c ]—was shown to be bicyclic with the Li⁺ cations bis‐S,Se‐chelated by the dianionic ligand. One‐electron oxidation of the dianions 4 b and 4 c with iodine afforded the diamagnetic complexes {[Li(TMEDA)]₂[(SPh₂P)₂CEEC(PPh₂S)₂]} ([Li(TMEDA)]₂ 7 b (E=S), [Li(TMEDA)]₂ 7 c (E=Se)), which are formally dimers of the radical anions [(E)C(PPh₂S)₂]^{? .} (E=S ( 5 b ), Se ( 5 c )) with elongated central E? E bonds. Two‐electron oxidation of the selenium‐containing dianion 4 c with I₂ yielded the LiI adduct of a neutral selone {[Li(TMEDA)][I(Se)C(PPh₂S)₂]}—[{LiI(TMEDA)} 6 c ]—whereas the analogous reaction with 4 b resulted in the formation of 7 b followed by protonation to give {[Li(TMEDA)][(SPh₂P)₂CSS(H)C(PPh₂S)₂]}—[Li(TMEDA)] 8 b . Attempts to identify the transient radicals 5 b and 5 c by EPR spectroscopy in conjunction with DFT calculations of the electronic structures of these paramagnetic species and their dimers are also described. The crystal structures of [{Li(TMEDA)}₂ 4 c ], [{LiI(TMEDA)} 6 c ] ? C₇H₈, [Li(TMEDA)]₂ 7 b? (CH₂Cl₂)_0.33, [Li(THF)₂]₂ 7 b , [Li(TMEDA)]₂ 7 c , [Li(TMEDA)] 8 b? (CH₂Cl₂)₂ and [Li([12]crown‐4)₂] 8 b were determined and salient structural features are discussed.     

Cobalt complexes of a selenium diimide and a tellurium diimide dimer

[CoCl₂{N,N′-Te₂(N^tBu)₄}] (1) was obtained in good yields by the reaction of equimolar amounts of (^tBu)NTe(μ-N^tBu)₂TeN(^tBu) and CoCl₂ in toluene under an argon atmosphere. The crystal structure of 1·CH₂Cl₂ showed that the dimeric tellurium diimide ligand is N,N′-chelated to cobalt. The related reaction of Se(N^tBu)₂ and CoCl₂ affords a green product tentatively identified as a 1:1 adduct [CoCl₂{N,N′-Se(N^tBu)₂}] (CHN analysis). However, recrystallization from thf produces the ion-separated complex [Co₂(μ-Cl)₃{N,N′-Se(N^tBu)₂}₂(thf)₂][CoCl₃{NH₂(^tBu)}]·1½thf (2·1½thf), in which the monomeric selenium diimide ligand is N,N′-chelated to cobalt in the cation. A pathway for the formation of 2 from [CoCl₂{N,N′-Se(N^tBu)₂}] in thf is proposed.     

Avoiding eddy-current problems in ultra-low-field MRI with self-shielded polarizing coils

In ultra-low-field magnetic resonance imaging (ULF MRI), superconductive sensors are used to detect MRI signals typically in fields on the order of 10-100 μT. Despite the highly sensitive detectors, it is necessary to prepolarize the sample in a stronger magnetic field on the order of 10-100 mT, which has to be switched off rapidly in a few milliseconds before signal acquisition. In addition, external magnetic interference is commonly reduced by situating the ULF-MRI system inside a magnetically shielded room (MSR). With typical dipolar polarizing coil designs, the stray field induces strong eddy currents in the conductive layers of the MSR. These eddy currents cause significant secondary magnetic fields that may distort the spin dynamics of the sample, exceed the dynamic range of the sensors, and prevent simultaneous magnetoencephalography and MRI acquisitions. In this paper, we describe a method to design self-shielded polarizing coils for ULF MRI. The experimental results show that with a simple self-shielded polarizing coil, the magnetic fields caused by the eddy currents are largely reduced. With the presented shielding technique, ULF-MRI devices can utilize stronger and spatially broader polarizing fields than achievable with unshielded polarizing coils.     

XHSTT: an XML archive for high school timetabling problems in different countries

We present the progress on the benchmarking project for high school timetabling that was introduced at PATAT 2008. In particular, we announce the High School Timetabling Archive XHSTT-2011 with 21 instances from 8 countries and an evaluator capable of checking the syntax of instances and evaluating the solutions.     

Scheduling a triple round robin tournament with minitournaments for the Finnish national youth ice hockey league

This paper presents a method to schedule a triple round robin tournament, which involves minitournaments, each hosted by one team. A key issue is that at the end of the season the number of home games should be balanced over the teams, despite the fact that in minitournament matches only the host team plays at home. This format is played in the Finnish national ice hockey league for players under the age of 20 years, where the problem is further complicated by many other constraints, for example, preassigned matches resulting from away tours that should limit the distances travelled by the teams. To obtain a schedule for this league, we sequentially solve four distinct combinatorial problems. This method allows us to construct a schedule for the 2009–2010 season, which is superior to the official schedule: it has no hard constraint violations, and outperforms the official schedule on three of five soft constraints.     

Using a time-delay and integration camera at a non-zero viewing angle under vibration conditions

The use of a TDI camera is restricted to cases of viewing from the direction of the surface normal. Our previous work indicated that a TDI camera can be used with viewing angles up to 30° from the surface normal which extends the usability of TDI for visual inspection applications. The objective of this paper is to examine the use of a TDI camera at a non-zero viewing angle under vibration conditions. The effects caused by vibration of the surface to be viewed become critical when using a TDI camera at non-zero viewing angles. A method of approximating the TDI performance under vibration conditions was determined and evaluated experimentally. The resulting measurements support the approximating method developed here.     

Interference and interactions in mesoscopic rings

We consider a mesoscopic ring connected to external reservoirs by tunnel junctions. The ring is capacitively coupled to an external gate electrode and may be pierced by a magnetic field. Due to strong electron–electron interactions within the ring the conductance shows Coulomb blockade oscillations as a function of the gate voltage, while Aharonov–Bohm interference effects lead to a dependence on the magnetic flux. The Hamiltonian of the ring is given by a Luttinger model that allows for an exact treatment of both interaction and interference effects. We conclude that the positions of conductance maxima as a function the external parameters can be used to determine the interaction parameter , and the shapes of conductance peaks are strongly affected by electron correlations within the ring.     

Asymptotics of Neumann harmonics when a cavity is close to the exterior boundary of the domain

We construct the asymptotics (as ε→0) of solutions to the Neumann problem for the Laplace equation and of the corresponding Dirichlet integral. The problem concerns a three-dimensional domain having two connected components of the boundary at the distance ε>0. To cite this article: G. Cardone et al., C. R. Mecanique 335 (2007).     

A note about Volterra operators on weighted Banach spaces of entire functions

We characterize boundedness, compactness and weak compactness of Volterra operators acting between different weighted Banach spaces of entire functions with sup‐norms in terms of the symbol g; thus we complement recent work by Bassallote, Contreras, Hernández‐Mancera, Martín and Paul 3 for spaces of holomorphic functions on the disc and by Constantin and Peláez 16 for reflexive weighted Fock spaces.