Diphenylcarbene Protected by Four ortho-Iodine Groups: An Unusually Persistent Triplet Carbene.

ABSTRACT: Diphenyldiazomethane with four iodine groups at the ortho positions and two tert-butyl groups at the para positions, i.e., bis(4-tert-butyl-2,6-diiodophenyl)diazomethane (1a-N?), was synthesized as a sterically hindered triplet carbene precursor. Irradiation of 1a-N? in solution effectively generated the corresponding triplet diphenylcarbene ³1a, which was characterized by UV-vis spectroscopy at low temperature, along with laser flash photolysis techniques at room temperature. The UV-vis spectrum of ³1a was obtained by irradiating 1a-N? in a 2-methyltetrahydrofuran matrix at 77 K. The ESR spectrum showed no triplet carbene signals, while a radical species was observed at the anticipated temperature of the decomposition of triplet carbene ³1a. Transient absorption bands ascribable to ³1a were observed by laser flash photolysis of 1a-N? in a degassed benzene solution and decayed very slowly with a second-order rate constant (2k/?l) of 5.5 × 10-³·s-¹. Steady-state irradiation of 1a-N? in degassed benzene afforded 9,10-diarylphenanthrene derivative 2a in a 31% yield. Triplet carbene ³1a was also trapped by either oxygen (kO2 = 6.5 × 10? M-¹·s-¹) or 1,4-cyclohexadiene (kCHD = 1.5 M-¹·s-¹) to afford the corresponding ketone 1a-O or the diarylmethane 1a-H?. The carbene was shown to be much less reactive than the triplet diphenylcarbene that is protected by two ortho-iodo and two ortho-bromo groups, ³1b.

SUBMITTER: Hirai K 

PROVIDER: S-EPMC6272868 | biostudies-other | 2016 Nov

REPOSITORIES: biostudies-other