The chemistry of arylnitrenes is dominated by their triplet ground states and excited open-shell singlet states. This results in radical-type reactions and unwanted rearrangements, which diminish the use of arylnitrenes as intermediates in organic synthesis. While the closed-shell singlet states of arylnitrenes are expected to undergo useful chemical transformations (comparable to the closed-shell singlet states of carbenes), these states are too high in energy to be chemically accessible. When triplet pentafluorophenylnitrene is interacting with the Lewis acid BF3 under the conditions of matrix isolation, a Lewis acid-base complex consisting of the closed-shell singlet state of the nitrene and two molecules of BF3 is formed. Although the closed-shell singlet state of pentafluorophenylnitrene is calculated (CCSD(T)) to lie more than 25 kcal/mol above its triplet ground state, the reaction with BF3 results in switching the spin state from triplet to singlet. The formation of the singlet complex was monitored by IR, UV-vis, and EPR spectroscopy. DFT, CCSD(T), and CASPT2 calculations confirm the experimental findings.
Switching the Spin State of Pentafluorophenylnitrene: Isolation of a Singlet Arylnitrene Complex
Costa, P.;
2018
Abstract
The chemistry of arylnitrenes is dominated by their triplet ground states and excited open-shell singlet states. This results in radical-type reactions and unwanted rearrangements, which diminish the use of arylnitrenes as intermediates in organic synthesis. While the closed-shell singlet states of arylnitrenes are expected to undergo useful chemical transformations (comparable to the closed-shell singlet states of carbenes), these states are too high in energy to be chemically accessible. When triplet pentafluorophenylnitrene is interacting with the Lewis acid BF3 under the conditions of matrix isolation, a Lewis acid-base complex consisting of the closed-shell singlet state of the nitrene and two molecules of BF3 is formed. Although the closed-shell singlet state of pentafluorophenylnitrene is calculated (CCSD(T)) to lie more than 25 kcal/mol above its triplet ground state, the reaction with BF3 results in switching the spin state from triplet to singlet. The formation of the singlet complex was monitored by IR, UV-vis, and EPR spectroscopy. DFT, CCSD(T), and CASPT2 calculations confirm the experimental findings.
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