Reaction of Triplet Phenylnitrene with Molecular Oxygen

Mieres‐Perez, Joel; Mendez‐Vega, Enrique; Velappan, Kavitha; Sander, Wolfram

doi:10.1021/acs.joc.5b01263

Cited by 45 publications

(57 citation statements)

References 32 publications

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“…Therefore, OPN is more reactive than N 2 O, as indicated by its reversible coupling reactionw ith CO, as nitrenes [28,29] and heavierp hosphinidenes [30] do. Given the very recently discovered reactions of nitrenes and phosphinidenes with other small molecules such as O 2 , [31] H 2 , [32] and H 2 O, [21b] their reactions with OPN, as ap otent interstellars pecies, [11a] should be of great interest, which are currently under investigations.…”

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confidence: 99%

Photochemistry of OPN: Formation of Cyclic PON and Reversible Combination with Carbon Monoxide

Song

Liu

et al. 2018

Chemistry A European J

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Cyclic PON, a first 16-electron triatomic ring consisting of two first-row elements, has been generated through 193 nm laser photolysis of OPN in cryogenic matrices. When the photolysis (365 nm) was performed in the presence of CO, OPN combines CO and furnishes an exotic acyclic molecule OPNCO. Upon the 193 nm laser irradiation, OPNCO dissociates mainly to OPN and CO with traces of PN and CO . The identification of cyclic PON and OPNCO with IR spectroscopy is supported by N-labeling experiments and quantum chemical calculations.

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confidence: 99%

Photochemistry of OPN: Formation of Cyclic PON and Reversible Combination with Carbon Monoxide

Song

Liu

et al. 2018

Chemistry A European J

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“…Matrix isolation experiments were performed by standard techniques as reported previously . The matrices were generated by co‐deposition of the precursors and a large excess of argon (Messer Griesheim, 99.99%).…”

Section: Methodsmentioning

confidence: 99%

Dinitreno pentaradicals: organic sextet molecules

Mieres‐Perez

Henkel

Mendez‐Vega

et al. 2016

J of Physical Organic Chem

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A new sextet ground state molecule, the 2,4,6‐trichloro‐1,3‐dinitrenophenoxyl radical, was obtained upon UV photolysis of the corresponding diazido precursor in argon at 5 K. The sextet molecule is formed stepwise with the triplet nitrene, the quartet nitreno radical, and the quintet dinitrene as intermediates that were detected by EPR spectroscopy. IR and UV–Vis measurements only allowed us to observe the main product, the quintet dinitrene. The coupling between the two nitrene centers and the oxygen centered radical in the sextet state results in zero‐field splitting (zfs) parameters of |D/hc| = 0.088 cm−1 and |E/hc| = 0.009 cm−1, considerably larger than in previously reported organic sextet molecules. An analogous sextet dinitrene formed by replacing the oxygen centered radical by a carbon centered radical was also studied by EPR spectroscopy, and in this case the zfs parameters |D/hc| = 0.125 cm−1 and |E/hc| = 0.023 cm−1 indicate even larger spin localization. Copyright © 2016 John Wiley & Sons, Ltd.

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“…10) (48)(49)(50)(51)(52). Nitroso oxide may arise from the spin-allowed reaction of triplet nitrene (53) with 3 O 2 and is a reaction analogous to that of triplet carbenes with 3 O 2 (54). Owing to its ability to hydroxylate toluene, nitroso oxide has been described as possessing diradical character (RN•OO•) (48)(49)(50)(51)(52).…”

Section: Mechanism Sectionmentioning

confidence: 99%

Density Functional Theory and ab Initio Computational Evidence for Nitrosamine Photoperoxides: Hammett Substituent Effects in the Photogeneration of the Nitrooxide Intermediate

Greer

Kwon

2018

Photochem & Photobiology

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Little attention has been focused on diradical and zwitterionic photoperoxides formed from nitrosamine compounds. Here, an attempt is made to probe the electronic character of the nitrooxide intermediate formed in photochemical reactions with triplet oxygen ( O ). Theoretical studies have been conducted to screen para-substituted phenyl nitrosamines. In particular, we find that electron-withdrawing substituents produce low-lying triplet nitrooxide diradicals. A clear electronic dependence in the S - T and S - S energy gaps of nitrooxides was found using Hammett plots. Computed geometries show a twisted diradical triplet nitrooxide moiety, which contrasts to the nearly flat singlet zwitterionic ground state nitrooxide moiety; analyses of charges (natural bond order), molecular orbitals (HOMO/LUMO) and spin densities enable these assignments. Calculations predict the former triplet species is photogenerated initially from nitrosamine with O . The conversion of the triplet nitrooxide diradical to the singlet ground state is an example where longer-lived zwitterionic nitrooxide structures become possible. The reaction mechanism is consistent with a zwitterionic ground state nitrooxide playing an important role in the bimolecular oxygen-transfer reaction with phosphine and phosphite trapping agents as has been observed experimentally.

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Reaction of Triplet Phenylnitrene with Molecular Oxygen

Cited by 45 publications

References 32 publications

Photochemistry of OPN: Formation of Cyclic PON and Reversible Combination with Carbon Monoxide

Photochemistry of OPN: Formation of Cyclic PON and Reversible Combination with Carbon Monoxide

Dinitreno pentaradicals: organic sextet molecules

Density Functional Theory and ab Initio Computational Evidence for Nitrosamine Photoperoxides: Hammett Substituent Effects in the Photogeneration of the Nitrooxide Intermediate

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