Photochemistry of protonated nitrosamine: chemical inertia of NH2NOH+ versus reactivity of NH3NO+

The Journal of Physical Chemistry. a
Daniel PeláezJuan Soto

Abstract

The photochemical behavior of the protonated simplest nitrosamine [NH2NO-H](+) has been addressed by means of the CASPT2//CASSCF methodology in conjunction with the ANO-L basis sets. The relative stability of the different tautomers, namely, (1) NH2NOH(+), (2) NH3NO(+), and (3) NH2NHO(+), has been considered, and the corresponding tautomerization transition states have been characterized. With respect to the most chemically relevant species, it has been found that NH2NOH(+) corresponds to a bound structure, while NH3NO(+) corresponds to an adduct between NH3 and NO(+) at both CASSCF and CASPT2 levels of theory. Vertical transition calculations and linear interpolations on the homolytic dissociation of NH3NO(+) in combination with previous results on neutral nitrosamine [J. Chem. Phys. 2006, 125, 164311] and neutral N,N-dimethylnitrosamine [J. Org. Chem. 2007, 72, 4741] indicate that, in acidic diluted solutions, the protonation of nitrosamine takes place on the excited surface. The N-N dissociation channels have been studied both in ground and first excited singlet state. An S1/S0 conical intersection is found to be responsible for the photostability of NH2NOH(+). On the contrary, NH3NO(+) is photochemically unstable as its fir...Continue Reading

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Citations

Jan 17, 2019·Physical Chemistry Chemical Physics : PCCP·Juan SotoDaniel Peláez
Feb 24, 2011·Chemistry : a European Journal·Wenjing SongAndreja Bakac
Dec 22, 2019·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Isabel López-TocónJuan Carlos Otero
Oct 14, 2010·The Journal of Physical Chemistry. a·Stig HellebustJohn R Sodeau
May 23, 2015·The Journal of Organic Chemistry·Marilene Silva OliveiraAlexander Greer

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