A highly delocalized triplet carbene, 5-Methylhexa-1,2,4-triene-1,3-diyl: matrix IR identification, structure, and reactions.
The first representative of highly delocalized triplet carbenes bearing both vinyl and ethynyl groups at the formal carbene center, 5-methylhexa-1,2,4-triene-1,3-diyl, has been generated in a low-temperature Ar matrix upon UV photolysis of 5-ethynyl-3,3-dimethyl-3H-pyrazole and detected by FTIR spectroscopy. The transformation of 3H-pyrazole into the carbene proceeds in two stages via intermediate 3-diazo-5-methylhex-4-en-1-yne. According to DFT PBE/TZ2P calculations, 5-methylhexa-1,2,4-triene-1,3-diyl possesses an effective conjugation along the five-carbon chain and shows the same type of the bond length alternation as the HC(4m+1)H-type polyacetylenic carbenes. The carbene readily reacts with molecular oxygen, producing carbonyl oxides, which undergo further transformations typical of this type of compound upon irradiation in the UV-visible region. Two major photolytic rearrangements of 5-methylhexa-1,2,4-triene-1,3-diyl represent reactions characteristic of vinyl carbenes and resulting in the formation of 1-ethynyl-3,3-dimethylcyclopropene and 3E-2-methylhexa-1,3-dien-5-yne. A minor reaction is that typical of ethynylcarbenes; this leads to the formation of singlet 2-(2-methylpropenyl)cyclopropenylidene. Fragments of singlet and triplet potential energy surfaces of the C(7)H(8) system have been explored in DFT PBE/TZ2P calculations.
Boganov
Sergey E
SE
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospekt 47, Moscow, Russian Federation 119991. serg.boganov@gmail.com
Faustov
Valery I
VI
Shavrin
Konstantin N
KN
Gvozdev
Valentin D
VD
Promyslov
Vladimir M
VM
Egorov
Mikhail P
MP
Nefedov
Oleg M
OM