Oxyallyl exposed: an open-shell singlet with picosecond lifetimes in solution but persistent in crystals of a cyclobutanedione precursor.

Photoinduced decarbonylation of 2,4-bis(spirocyclohexyl)-1,3-cyclobutanedione 1 in the crystalline solid state resulted in formation of a deep blue transient with λ(max) = 550 nm and a half-life of 42 min at 298 K, identified as kinetically stabilized oxyallyl. Support for an open-shell singlet species was obtained by spectroscopic analysis and (4/4) CASSCF calculations with the 6-31+G(d) basis set and multireference MP2 corrections. The electronic spectrum of the singlet biradical, confirmed by femtosecond pump-probe studies in solution, was matched by coupled cluster calculations with single and double corrections.

Mechanistic aspects of the formation of aldehydes and nitriles in photosensitized reactions of aldoxime ethers.

The photooxidation of a series of aldoxime ethers was studied by laser flash photolysis and steady-state (product studies) methods. Nanosecond laser flash photolysis studies have shown that chloranil (CA)-sensitized reactions of the O-methyl (1), O-ethyl (2), O-benzyl (3), and O-tert-butyl (4) benzaldehyde oximes result in the formation of the corresponding radical cations. In polar non-nucleophilic solvents such as acetonitrile, there are several follow-up pathways available depending on the structure of the aldoxime ether and the energetics of the reaction pathway.

Photosensitized reactions of oxime ethers: a steady-state and laser flash photolysis study.

The mechanistic aspects of the photosensitized reactions of a series of oxime ethers were studied by steady-state (product studies) and laser flash photolysis methods. Nanosecond laser flash photolysis studies have shown that chloranil-sensitized reactions of the oxime ethers result in the formation of the corresponding radical cations. The radical cation species react with nucleophiles such as MeOH by clean second-order kinetics with rate constants of (0.