Photoelimination of Nitrogen from Diazoalkanes: Involvement of Higher Excited Singlet States in the Carbene Formation

Piteša, Tomislav; Alešković, Marija; Becker, Kristin; Basarić, Nikola; Došlić, Nađa (2020) Photoelimination of Nitrogen from Diazoalkanes: Involvement of Higher Excited Singlet States in the Carbene Formation. Journal of the American Chemical Society, 142 (21). pp. 9718-9724. ISSN 0002-7863

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Abstract

Although diazoalkanes are important carbene precursors in organic synthesis, a comprehensive mechanism of photochemi-cal formation of carbenes from diazoalkanes has not been proposed. Synergy of experiments and computations demon-strates the involvement of higher excited singlet states in the photochemistry of diazoalkanes. In all investigated diazo-alkanes, excitation to S1 results in nonreactive internal conversion to S0. On the contrary, excitation to higher-lying singlet states (Sn, n > 1), drives the reaction toward a different segment of the S1/S0 conical intersection seam and results in nitrogen elimination and formation of carbenes.

Item Type:	Article
Uncontrolled Keywords:	Diazoalkanes ; Carbenes ; Anti-Kasha Photochemistry
Subjects:	NATURAL SCIENCES > Chemistry NATURAL SCIENCES > Chemistry > Theoretical Chemistry NATURAL SCIENCES > Chemistry > Organic Chemistry
Divisions:	Division of Organic Chemistry and Biochemistry Division of Physical Chemistry
Projects:	Project title Project leader Project code Project type Supramolekulska kontrola fotokemijskih reakcija eliminacije Basarić, Nikola IP-2014-09-6312 HRZZ Svjetlo na molekulama: istraživanje spregnute elektronske i nuklearne dinamike Došlić, Nađa IP-2016-06-1142 HRZZ
Depositing User:	Nikola Basarić
Date Deposited:	16 Nov 2021 11:09
URI:	http://fulir.irb.hr/id/eprint/6683
DOI:	10.1021/jacs.0c02221

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