RESUMEN
A series of nickel(II) porphyrins bearing one or two bulky nitrogen donors at the meso positions were prepared by using Ullmann methodology or more classical Buchwald-Hartwig amination reactions to create the new C-N bonds. For several new compounds, single crystals were obtained, and the X-ray structures were solved. The electrochemical data of these compounds are reported. For a few representative examples, spectroelectrochemical measurements were used to clarify the electron exchange process. In addition, a detailed electron paramagnetic resonance (EPR) study was performed to estimate the extent of delocalization of the generated radical cations. In particular, electron nuclear double resonance spectroscopy (ENDOR) was used to determine the coupling constants. DFT calculations were conducted to corroborate the EPR spectroscopic data.
Asunto(s)
Porfirinas , Espectroscopía de Resonancia por Spin del Electrón , Modelos Moleculares , Aminas , Rayos XRESUMEN
Nitriles are recurring motifs in bioactive molecules and versatile functional groups in synthetic chemistry. Despite recent progress, direct introduction of a nitrile moiety in heteroarenes remains challenging. Recent developments in electrochemical reactions pave the way to more practical cyanation protocols. However, currently available methods typically require hazardous cyanide sources, expensive mediators, and often suffer from narrow substrate scope and laborious reaction set-up. To address the limitations of current synthetic methods, herein, an effective, sustainable, and scalable procedure for the direct C(sp2 )-H cyanation of aromatic N-heterocycles with a user-friendly flow-electrochemical set-up is reported. Furthermore, high substrate and functional-group tolerance is demonstrated, allowing late-stage functionalization of drug-like scaffolds, such as natural products and pharmaceuticals.
Asunto(s)
Productos Biológicos , Nitrilos , CianurosRESUMEN
Nanostructures were built at the solid/liquid interface by self-assembly and/or coordination bonds. Metalloporphyrins bearing two external coordination sites and long alkyl chains allowed the self-assembly of the compounds on highly oriented pyrolitic graphite. After addition of a metal ion, long transition-metal linked porphyrin nanoribbons were obtained and visualized by scanning tunneling microscopy. In these porphyrin ribbons electronic delocalization is possible through the d orbitals of the connecting metal ions.
RESUMEN
Several porphyrin dimers linked by metal ions were prepared. One trimeric compound was also isolated and one porphyrin dimer linked by palladium(II) could be structurally characterized. In solution, the size of the new compounds was estimated by DOSY NMR techniques. These compounds all contained long aliphatic chains (O-C12H25), which were used to assemble them at a highly oriented pyrolytic graphite (HOPG)/liquid interface. The highly ordered arrays were visualized by scanning tunneling microscopy (STM).