Halogen Derivatives of m -Phenylene(carbeno)nitrene: A Switch in Ground-State Multiplicity
2002; American Chemical Society; Volume: 67; Issue: 16 Linguagem: Inglês
10.1021/jo025877q
ISSN1520-6904
AutoresTomonori Enyo, Athanassios Nicolaides, Hideo Tomioka,
Tópico(s)Photochemistry and Electron Transfer Studies
Resumom-Phenylene-coupled carbenonitrenes [(3-nitrenophenyl)methylene (2-H), (3-nitrenophenyl)fluoromethylene (2-F), (3-nitrenophenyl)chloromethylene (2-Cl), (3-nitrenophenyl)bromomethylene (2-Br)] have been investigated computationally (with B3LYP, MCSCF, CASPT2, ROMP2, and QCISD(T) methods) and experimentally (with IR, UV, and ESR spectroscopy). For each species, five electronic states were considered. At the highest level of theory explored, the parent compound (2-H) has a quintet ground state, but its halogen derivatives (2-X, X = F, Cl, and Br) have triplet ground states. A linear relationship between the Q−T energy gap of 2-X and the T−S gap of the corresponding phenylcarbenes 8-X is found, which can be helpful in rationalizing and predicting ground-state multiplicities in m-phenylene-linked carbenonitrenes and similar species. Precursors for the photochemical generation of 2-X (X = H, F, Cl, and Br) were synthesized and photolyzed in matrixes (Ar, triacetin) at low temperatures. IR (Ar, 13 K) and ESR (triacetin, 77 K) data are compatible with the generation of triplet halocarbenonitrenes 2-X, (X = F, Cl, and Br). All four compounds upon further irradiation undergo isomerization to substituted cyclopropenes 5-X (X = H, F, Cl, and Br), as suggested by their IR spectra.
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