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Mechanism of the photodissociation of 4-diphenyl( trimethylsilyl)methyl-N,N-dimethylaniline
(EN)
Tasis, D. A.
(EN)
Πανεπιστήμιο Ιωαννίνων. Σχολή Θετικών Επιστημών. Τμήμα Χημείας
(EL)
Tasis, D. A.
(EN)
On irradiation in hexane (248- and 308-nm laser light) 4-diphenyl(trimethylsilyl)methyl-N,N-dimethylaniline, undergoes photodissociation of the C-Si bond giving 4-N,N-dimethylamino-triphenylmethyl radical, 3(.) (lambda(max) at 343 and 403 nm), in very high quantum yield (Phi = 0.92). The intervention of the triplet state of 2 (lambda(max) at 515 nm) is clearly demonstrated through quenching experiments with 2,3-dimethylbuta-1,3-diene, styrene, and methyl methacrylate using nanosecond laser flash photolysis (LFP). The formation of 3(.) is further demonstrated using EPR spectroscopy. The detection of the S-1 state of 2 was achieved using 266-nm picosecond LFP, and its lifetime was found to be 1400 ps. in agreement with the fluorescence lifetime (tau(f) = 1500 ps, Phi(f) = 0.085). The S-1 state is converted almost exclusively to the T-1 state (Phi T = 0.92). In polar solvents such as MeCN, 2 undergoes (1) photoionization to its radical cation 2(.+), and (2) photodissociation of the C-Si bond, giving radical 3(.) as before in hexane. The formation of 2(.+) occurs through a two-photon process. Radical cation 2(.+) does not fragment further, as would be expected, to 3(.) via a nucleophile(MeCN)assisted C-Si bond cleavage but regenerates the parent compound 2. Obviously, the bulkiness of the triphenylmethyl group prevents interaction of 2(.+) with the solvent (MeCN) and transfer to it of the electrofugal group Me3Si+. The above results of the laser flash photolysis are supported by pulse radiolysis, fluorescence measurements, and product analysis.
(EN)
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