RESUMEN
Ruthenium-silica hybrid material (RuCl2(PR3)2-2-PyCH-AMPTSi/SiO2) was prepared and characterized by various spectroscopic techniques. A deconvolution procedure was applied to the spectroscopic data to deconstruct the overlapped bands. A density functional theoretical approach was applied to get insights into the electronic structure of the ruthenium coordination site and the functional RI-PBE-D3/Def2TZVP basis set was used for the optimization. Relativistic effects were considered using the zero-order regular approximation (ZORA). The anchoring process, evinced for each step of the synthesis of the hybrid material, was tracked by FT-IR analyses. The transitions observed in the FT-IR spectra were verified by DFT analyses, which agree with the experimental data. In the DRS-UV-Vis spectra, three main bands were detected by the deconvolution procedure that correspond to the charge transfer transitions, with the main contributions from ruthenium-chlorine and imine-pyridine fragments. TD-DFT results reveal that ruthenium-chlorine antibonding orbitals act as main charge donors, while pyridine-imine is the main charge acceptor.
RESUMEN
The nickel-catalyzed N-alkylation of a variety of arylamines via transfer hydrogenation in the absence of pressurized hydrogen and basic or acidic additives was achieved in a tandem reaction. This process was further extended to the C[double bond, length as m-dash]N bond reduction and N-alkylation of a variety of imines with ethanol, the latter acting as a hydrogen and acetaldehyde source, which allowed for the reduction and subsequent condensation to yield the corresponding N-alkylated products.