Aromatic C–H bond activation revealed by infrared multiphoton dissociation spectroscopy

Abstract

Metal-oxide cations are models of catalyst mediating the C-H bond activation of organic substrates. One of the most powerful reagents suggested in the gas phase is based on CuO(+) . Here, we describe the activation of the aromatic C-H bonds of phenanthroline in its complex with CuO(+) . The reaction sequence starts with a hydrogen atom abstraction by the oxygen atom from the 2-position of the phenanthroline ring, followed by OH migration to the ring. Using infrared multiphoton spectroscopy, it is shown that the reaction can be energetically facilitated by additional coordination of a water ligand to the copper ion. As the reaction is intramolecular, a spectroscopic characterization of the product is mandatory in order to unambiguously address the reaction mechanism.

Closed Shell Iron(IV) Oxo Complex with an Fe–O Triple Bond: Computational Design, Synthesis, and Reactivity

“…However,t he resulting complex was unreactive and its IRPD spectrum did not show any Fe-O stretching (n(Fe-O)) vibration ( Figure S4 in the Supporting Information). We hypothesized that aromatic hydroxylation of one of the pyridines might have occurred, [47] possibly via ar oll-over mechanism. [48,49] To enhance the stability of the singlet spin state and to prevent the ligand oxidation, we performed screening of functional groups that could substitute the pyridine rings at the acridone skeleton.…”

Carboxylate-assisted C–H activation of phenylpyridines with copper, palladium and ruthenium: a mass spectrometry and DFT study

“…By comparison, the isomer that was isolated and analyzed in the gas phase can then be matched with one or multiple of the theoretical possibilities allowing for direct identification. 79 – 84 …”

Assessment of climate change impacts on the hydrology of the Peruvian Amazon–Andes basin

“…These results imply that CH bond activation is facile and occurs already with the loss of NO 2 . and not only during CID of m / z 391 23. Hence, it appears that NO 2 .…”