Carbenes and Nitrenes

E. Gras (1) , Stefan Chassaing (2)

1 LCC - Laboratoire de chimie de coordination
2 ITAV - Institut des Technologies Avancées en sciences du Vivant

This chapter discusses the chemistry and spectroscopic studies of heteroarylcarbenes. It describes the formation of carbenes bearing six-membered ring heterocycles mainly pyridyl- and diazafluorenyl-carbenes from their diazirine precursors and addresses their reactivities and electron paramagnetic resonance (EPR) spectroscopy as well as their thermal and photochemical rearrangements. The effect of electron-withdrawing groups on the stability of singlet carbenes has been explored computationally as a comparison to their conjugate acid, the carbenium ions. The electrophilic, ambiphilic and nucleophilic characters of a range of singlet carbenes have been compared to their ‘intrinsic reactivity index’. The generation and the evaluation of the singlet-triplet gap have been investigated by density functional theory (DFT) and CCSD (T) calculations for an array of carbenes and nitrenes. Trimetallic palladium and gold carbene complexes structured around a triphenylene scaffold have been synthesized and used in α-arylation of propiophenone, Suzuki-Miyaura reactions and hydroamination of acetylene.

Mots clés: density functional theory dicopper alkylnitrenes electron paramagnetic resonance spectroscopy intrinsic reactivity index nucleophilic carbenes propiophenone Suzuki-Miyaura reactions trimetallic palladium

Domaines: Chimie de coordination

E. Gras, Stefan Chassaing. Carbenes and Nitrenes. Knipe, A. C. Organic Reaction Mechanisms-2013: An annual survey covering the literature dated january to december 2013, 4, John Wiley & Sons, pp.177-215, 2016, 978-1-118-70786-9. ⟨hal-02042484⟩