N‐Heterocyclic Silylenes in Boron Chemistry: Facile Formation of Silylboranes and Silaborinines

Reaction of a N‐heterocyclic silylene (NHSi) with PhBX₂ (X=Cl, Br) readily afforded six‐membered silaborinines through an insertion/ring expansion sequence. Increasing the sterics of the borane from phenyl to duryl enabled the selective generation and isolation of the highly colored silylborane intermediates. Theoretical studies on the mechanism and energetics of the silaborinine formation were fully consistent with the experimental observations.     

Toluene as a novel carrier of xanthates—preparation,use and surrogate of S-tri- and di-chloromethyl xanthates

Toluene has been identified as a novel carrier of xanthates. Their corresponding fragmentative precursors proved to behave efficiently in radical group transfer reactions. As examples, unprecedented S-tri/di-chloromethyl xanthates could be prepared, isolated and further used in radical additions to olefins. Their precursors (de-aromatized toluene upon which is grafted, at one end, a tri/di-chloromethyl-group and, at the other end, a dithiocarbonyl group) can also be used directly in the transfer of both groups to olefins. The re-aromatizing loss of toluene by radical initiated fragmentation of the precursors brings thus new opportunities to the chemistry of xanthates, exemplified here in the intermolecular additions to olefins of new S-tri/di-chloromethyl xanthates.     

A two-sided short-recurrence extended Krylov subspace method for nonsymmetric matrices and its relation to rational moment matching

The Lagrange interpolation problem on spaces of symmetric bivariate polynomials is considered to reduce the interpolation problem to problems of approximately half dimension. The Berzolari-Radon construction is adapted to these kinds of problems by considering nodes placed on symmetric lines or symmetric pairs of lines. A Newton formula for the symmetric interpolant using the Berzolari-Radon construction is proposed.     

Synthesis and Coordination Behavior of a New Hybrid Bidentate Ligand with Phosphine and Silylene Donors

This work describes the synthesis and coordination behavior of a new mixed-donor ligand PhC(NtBu)₂SiC₆H₄PPh₂ ( 1 ) containing both silylene and phosphine donor sites. Ligand 1 was synthesized from a reaction of ortho-lithiated diphenylphosphinobenzene (LiC₆H₄PPh₂) with chlorosilylene (PhC(NtBu)₂SiCl). Treatment of 1 with Se and GeCl₂ resulted in Si^IV compounds 2 and 3 by selective oxidation of the silylene donor. This strong σ-donor ligand induces dissociation of CuCl and PhBCl₂ leading to formation of ionic complexes 4 and 5 respectively. The reaction of 1 with ZnCl₂ and AlCl₃ resulted in the formation of chelate complexes 5 and 7 , respectively, while treatment with EtAlCl₂ and GaCl₃ forms monodentate complexes 8 and 9 . X-ray analysis of 4 showed that the copper is in the spiro center of the two five-membered rings. Moreover, the copper(I)chloride has not been oxidized but dissociates to Cu⁺ and [CuCl₂]⁻. All the compounds are well characterized by mass spectrometry, elemental analysis, NMR spectroscopy, and single-crystal X-ray diffraction studies.     

Anomalous lattice response at the Mott transition in a quasi-2D organic conductor

Discontinuous changes of the lattice parameters at the Mott metal-insulator transition are detected by high-resolution dilatometry on deuterated crystals of the layered organic conductor kappa-(BEDT-TTF)(2)Cu[N(CN)(2)]Br. The uniaxial expansivities uncover a striking and unexpected anisotropy, notably a zero effect along the in-plane c axis along which the electronic interactions are relatively strong. A huge thermal expansion anomaly is observed near the end point of the first-order transition line enabling us to explore the critical behavior with very high sensitivity. The analysis yields critical fluctuations with an exponent alpha approximately 0.8+/-0.15 at odds with the novel criticality recently proposed for these materials [Kagawa et al., Nature (London) 436, 534 (2005)]. Our data suggest an intricate role of the lattice degrees of freedom in the Mott transition for the present materials.     

Acid‐Catalyzed Oxidative Radical Addition of Ketones to Olefins

Based on a mechanistic study, we have discovered a Brønsted acid catalyzed formation of ketone radicals. This is believed to proceed via thermally labile alkenyl peroxides formed in situ from ketones and hydroperoxides. The discovery could be utilized to develop a multicomponent radical addition of unactivated ketones and tert‐butyl hydroperoxide to olefins. The resulting γ‐peroxyketones are synthetically useful intermediates that can be further transformed into 1,4‐diketones, homoaldol products, and alkyl ketones. A one‐pot reaction yielding a pharmaceutically active pyrrole is also described.     

Optimization of residence time distribution in RCDG and an assessment of its applicability in continuous manufacturing

Knowledge of residence time is a critical aspect in developing control and material diversion strategies for continuous manufacturing processes in pharmaceutica...