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Pregled bibliografske jedinice broj: 1266415

Ultrafast Photoelimination of Nitrogen from Upper Excited States of Diazoalkanes and the Fate of Carbenes Formed in the Reaction


Brusar, Vedran; Forjan, Mateo; Ljubić, Ivan; Alešković, Marija; Becker, Kristin; Vdović, Silvije
Ultrafast Photoelimination of Nitrogen from Upper Excited States of Diazoalkanes and the Fate of Carbenes Formed in the Reaction // Journal of organic chemistry, 88 (2023), 7; 4286-4300 doi:10.1021/acs.joc.2c02875 (međunarodna recenzija, članak, znanstveni)


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Naslov
Ultrafast Photoelimination of Nitrogen from Upper Excited States of Diazoalkanes and the Fate of Carbenes Formed in the Reaction

Autori
Brusar, Vedran ; Forjan, Mateo ; Ljubić, Ivan ; Alešković, Marija ; Becker, Kristin ; Vdović, Silvije

Izvornik
Journal of organic chemistry (0022-3263) 88 (2023), 7; 4286-4300

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
absorption ; carbene compounds ; excited states ; hydrocarbons ; time-dependent density functional theory

Sažetak
The photochemical reactivity of diphenyldiazomethane 1 and phenyl 1- and 2 adamantyl diazomethanes 2 and 3, respectively, was investigated by transient absorption spectroscopy (TA). Photoelimination of N2 upon UV excitation takes place in the anti-Kasha ultrafast photochemical reaction from the upper excited singlet states to deliver singlet carbenes, which were, in the case of 1 and 2, detected by fs-TA. The reactivity of the carbenes differs with respect to the substituent at the carbene center. The singlet car-1 in a nonpolar solvent delivers the triplet carbene by intersystem crossing (ISC). Singlet car-2 does not undergo ISC but reacts in the intermolecular insertion reactions into C–H bonds. Car-3 has an α-C–H bond next to the carbene center and reacts rapidly in the intramolecular C– H insertion reaction to deliver alkene, precluding its detection by fs-TA. However, the isolation of ketone photoproducts from 3 is highly indicative of triplet car-3’s intermediate formation. The TA spectra from the S1–S3 states of 1–3 were computed using time-dependent density functional theory, while the multiconfigurational perturbation theory to the second order was used for the absorption spectra of the corresponding singlet and triplet carbenes. The modeled and measured spectra are in good agreement, and the computations corroborate the assignments of the key short-lived intermediates.

Izvorni jezik
Engleski

Znanstvena područja
Fizika, Kemija, Interdisciplinarne prirodne znanosti



POVEZANOST RADA


Projekti:
UIP-2017-05-5831 - Grupa za primijenjenu ultrabrzu spektroskopiju i fotokemijsku identifikaciju (GASPI) (Vdović, Silvije, HRZZ - 2017-05) ( CroRIS)
--IP-2020-02-9932 - Efekt kvantnog tuneliranja: dinamika molekula s kvantnim jezgrama (QuanTunMol) (Cvitaš, Marko Tomislav) ( CroRIS)
IP-2014-09-6312 - Supramolekulska kontrola fotokemijskih reakcija eliminacije (SupraPhotoE) (Basarić, Nikola, HRZZ - 2014-09) ( CroRIS)
--IP-2019-04-8008 - Fotokemija: Reakcijski mehanizmi i primjene u organskoj sintezi i biologiji (PhotoApp) (Basarić, Nikola) ( CroRIS)

Ustanove:
Institut za fiziku, Zagreb,
Institut "Ruđer Bošković", Zagreb

Profili:

Avatar Url Ivan Ljubić (autor)

Avatar Url Silvije Vdović (autor)

Avatar Url Vedran Brusar (autor)

Avatar Url Marija Alešković (autor)

Avatar Url Mateo Forjan (autor)

Poveznice na cjeloviti tekst rada:

Pristup cjelovitom tekstu rada doi pubs.acs.org

Citiraj ovu publikaciju:

Brusar, Vedran; Forjan, Mateo; Ljubić, Ivan; Alešković, Marija; Becker, Kristin; Vdović, Silvije
Ultrafast Photoelimination of Nitrogen from Upper Excited States of Diazoalkanes and the Fate of Carbenes Formed in the Reaction // Journal of organic chemistry, 88 (2023), 7; 4286-4300 doi:10.1021/acs.joc.2c02875 (međunarodna recenzija, članak, znanstveni)
Brusar, V., Forjan, M., Ljubić, I., Alešković, M., Becker, K. & Vdović, S. (2023) Ultrafast Photoelimination of Nitrogen from Upper Excited States of Diazoalkanes and the Fate of Carbenes Formed in the Reaction. Journal of organic chemistry, 88 (7), 4286-4300 doi:10.1021/acs.joc.2c02875.
@article{article, author = {Brusar, Vedran and Forjan, Mateo and Ljubi\'{c}, Ivan and Ale\v{s}kovi\'{c}, Marija and Becker, Kristin and Vdovi\'{c}, Silvije}, year = {2023}, pages = {4286-4300}, DOI = {10.1021/acs.joc.2c02875}, keywords = {absorption, carbene compounds, excited states, hydrocarbons, time-dependent density functional theory}, journal = {Journal of organic chemistry}, doi = {10.1021/acs.joc.2c02875}, volume = {88}, number = {7}, issn = {0022-3263}, title = {Ultrafast Photoelimination of Nitrogen from Upper Excited States of Diazoalkanes and the Fate of Carbenes Formed in the Reaction}, keyword = {absorption, carbene compounds, excited states, hydrocarbons, time-dependent density functional theory} }
@article{article, author = {Brusar, Vedran and Forjan, Mateo and Ljubi\'{c}, Ivan and Ale\v{s}kovi\'{c}, Marija and Becker, Kristin and Vdovi\'{c}, Silvije}, year = {2023}, pages = {4286-4300}, DOI = {10.1021/acs.joc.2c02875}, keywords = {absorption, carbene compounds, excited states, hydrocarbons, time-dependent density functional theory}, journal = {Journal of organic chemistry}, doi = {10.1021/acs.joc.2c02875}, volume = {88}, number = {7}, issn = {0022-3263}, title = {Ultrafast Photoelimination of Nitrogen from Upper Excited States of Diazoalkanes and the Fate of Carbenes Formed in the Reaction}, keyword = {absorption, carbene compounds, excited states, hydrocarbons, time-dependent density functional theory} }

Časopis indeksira:


  • Current Contents Connect (CCC)
  • Web of Science Core Collection (WoSCC)
    • Science Citation Index Expanded (SCI-EXP)
    • SCI-EXP, SSCI i/ili A&HCI
  • Scopus
  • MEDLINE


Citati:





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