PtII-Catalyzed Hydroxylation of Terminal Aliphatic C(sp3)−H Bonds with Molecular Oxygen

The practical application of Shilov-type Pt catalysis to the selective hydroxylation of terminal aliphatic C−H bonds remains a formidable challenge, due to difficulties in replacing Pt^IV with a more economically viable oxidant, particularly O₂. We report the potential of employing FeCl₂ as a suitable redox mediator to overcome the kinetic hurdles related to the direct use of O₂ in the Pt reoxidation. For the selective conversion of butyric acid to γ-hydroxybutyric acid (GHB), a significantly enhanced catalyst activity and stability (turnover numbers (TON)>30) were achieved under 20 bar O₂ in comparison to current state-of-the-art systems (TON<10). In this regard, essential reaction parameters affecting the overall activity were identified, along with specific additives to attain catalyst stability at longer reaction times. Notably, deactivation by reduction to Pt⁰ was prevented by the addition of monodentate pyridine derivatives, such as 2-fluoropyridine, but also by introducing varying partial pressures of N₂ in the gaseous atmosphere. Finally, stability tests revealed the involvement of Pt^II and FeCl₂ in catalyzing the non-selective overoxidation of GHB. Accordingly, in situ esterification with boric acid proved to be a suitable strategy to maintain enhanced selectivities at much higher conversions (TON>60). Altogether, a useful catalytic system for the selective hydroxylation of primary aliphatic C−H bonds with O₂ is presented.     

RLS-based initialization for per-tone equalizers in DMT receivers

Per-tone equalization has recently been proposed as an alternative receiver structure for discrete multitone-based systems improving upon the well-known structure based on time-domain equalization. Fast initialization of all the equalizer coefficients has been identified as an open problem. In this letter, a recursive initialization scheme based on recursive least squares with inverse updating is presented for the per-tone equalizers. Simulation results show convergence with an acceptably small number of training symbols. Complexity calculations are made for per-tone equalization and for the case where tones are grouped. It is demonstrated with an example that in the latter case, initialization complexity becomes sufficiently low and comparable to complexity during data transmission.     

Finite element analysis of electromagnetic scattering from a cavity

A finite element method (FEM) is implemented to compute the radar cross section of a two-dimensional (2D) cavity embedded in an infinite ground plane. The method is based on the variational formulation which uses the Fourier transform to couple the fields outside the cavity and those inside the cavity; hence, the scattering problem can be reduced to a bounded domain. The convergence of the discrete finite element problem is analyzed. Numerical results are presented and compared with those obtained by the standard finite element-Green function method and by the 2D integral equation method.