Ma, Xin published the artcileProtonated Ground-State Singlet meta-Pyridynes React from an Excited Triplet State, Quality Control of 123-39-7, the main research area is protonated meta pyridyne singlet ground triplet excited state reactivity.
The gaseous 2,6-didehydropyridinium cation and its derivatives transfer a proton to reagents for which the reaction for their singlet ground states is too endothermic to be observed These reactions occur from the lowest-energy excited triplet states, which has not been observed (or reported) for other meta-benzyne analogs. Quantum chem. calculations indicate that the (excited) triplet states are stronger Bronsted acids than their (ground) singlet states, likely due to unfavorable three-center, four-electron interactions in the singlet-state conjugate bases. The cations have substantially smaller (calculated) singlet-triplet (S-T) splittings (ranging from ca. -11 to -17 kcal mol-1) than other related meta-benzyne analogs (e.g., -23.4 kcal mol-1 for the 3,5-isomer). This is rationalized by the destabilization of the singlet states (relative to the triplet states) by reduced (spatial) overlap of the nonbonding MOs due to the presence of the nitrogen atom between the radical sites (making the ring more rigid). Both the singlet and triplet states are believed to be generated upon formation of these biradicals via energetic collisions due to their small S-T splittings. It appears that once the triplet states are formed, the rate of proton transfer is faster than the rate of intersystem crossing unless the biradicals contain heavy atoms.
Journal of Organic Chemistry published new progress about Crystal structure. 123-39-7 belongs to class amides-buliding-blocks, name is N-Methylformamide, and the molecular formula is C2H5NO, Quality Control of 123-39-7.
Referemce:
Amide – Wikipedia,
Amide – an overview | ScienceDirect Topics