Generation and direct observation of a triplet arylnitrenium ion

Lili Du, Juanjuan Wang, Yunfan Qiu, Runhui Liang, Penglin Lu, Xuebo Chen (), David Lee Phillips () and Arthur H. Winter ()
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Lili Du: Jiangsu University
Juanjuan Wang: Beijing Normal University
Yunfan Qiu: Iowa State University
Runhui Liang: The University of Hong Kong
Penglin Lu: The University of Hong Kong
Xuebo Chen: Beijing Normal University
David Lee Phillips: The University of Hong Kong
Arthur H. Winter: Iowa State University

Nature Communications, 2022, vol. 13, issue 1, 1-9

Abstract: Abstract Nitrenium ions are important reactive intermediates in both chemistry and biology. Although singlet nitrenium ions are well-characterized by direct methods, the triplet states of nitrenium ions have never been directly detected. Here, we find that the excited state of the photoprecursor partitions between heterolysis to generate the singlet nitrenium ion and intersystem crossing (ISC) followed by a spontaneous heterolysis process to generate the triplet p-iodophenylnitrenium ion (np). The triplet nitrenium ion undergoes ISC to generate the ground singlet state, which ultimately undergoes proton and electron transfer to generate a long-lived radical cation that further generates the reduced p-iodoaniline. Ab Initio calculations were performed to map out the potential energy surfaces to better understand the excited state reactivity channels show that an energetically-accessible singlet-triplet crossing lies along the N-N stretch coordinate and that the excited triplet state is unbound and spontaneously eliminates ammonia to generate the triplet nitrenium ion. These results give a clearer picture of the photophysical properties and reactivity of two different spin states of a phenylnitrenium ion and provide the first direct glimpse of a triplet nitrenium ion.

Date: 2022
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DOI: 10.1038/s41467-022-31091-z

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