Photooxygenations of PhSMe and Bu(2)S sensitized by N-methylquinolinium (NMQ(+)) and 9,10-dicyano-anthracene (DCA) in O(2)-saturated MeCN have been investigated by laser and steady-state photolysis. Laser photolysis experiments showed that excited NMQ(+) promotes the efficient formation of sulfide radical cations with both substrates either in the presence or in absence of a cosensitizer (toluene). In contrast, excited DCA promotes the formation of radical ions with PhSMe, but not with Bu(2)S. To observe radical ions with the latter substrate, the presence of a cosensitizer (biphenyl) was necessary. With Bu(2)S, only the dimeric form of the radical cation, (Bu(2)S)(2)(+.), was observed, while the absorptions of both PhSMe(+.) and (PhSMe)(2)(+.) were present in the PhSMe time-resolved spectra. The decay of the radical cations followed second-order kinetics, which in the presence of O(2), was attributed to the reaction of the radical cation (presumably in the monomeric form) with O(2)(-.) generated in the reaction between NMQ(.) or DCA(-.) and O(2). The fluorescence quenching of both NMQ(+) and DCA was also investigated, and it was found that the fluorescence of the two sensitizers is efficiently quenched by both sulfides (rates controlled by diffusion) as well by O(2) (k(q) = 5.9 x 10(9) M(-1) s(-1) with NMQ(+) and 6.8 x 10(9) M(-1) s(-1) with DCA). It was also found that quenching of (1)NMQ(*) by O(2) led to the production of (1)O(2) in significant yield (phi(Delta) = 0.86 in O(2)-saturated solutions) as already observed for (1)DCA(*). The steady-state photolysis experiments showed that the NMQ(+)- and DCA-sensitized photooxygenation of PhSMe afford exclusively the corresponding sulfoxide. A different situation holds for Bu(2)S: with NMQ(+), the formation of Bu(2)SO(2) was accompanied by that of small amounts of Bu(2)S(2); with DCA, the formation of Bu(2)SO(2) was also observed. It was conclusively shown that with both sensitizers, the photooxygenations of PhSMe occur by an electron transfer (ET) mechanism, as no sulfoxidation was observed in the presence of benzoquinone (BQ), which is a trap for O(2)(-.) NMQ(.), and DCA(-.). BQ also suppressed the NMQ(+)-sensitized photooxygenation of Bu(2)S, but not that sensitized by DCA, indicating that the former is an ET process, whereas the second proceeds via singlet oxygen. In agreement with the latter conclusion, it was also found that the relative rate of the DCA-induced photooxygenation of Bu(2)S decreases by increasing the initial concentration of the substrate and is slowed by DABCO (an efficient singlet oxygen quencher). To shed light on the actual role of a persulfoxide intermediate also in ET photooxygenations, experiments in the presence of Ph(2)SO (a trap for the persulfoxide) were carried out. Cooxidation of Ph(2)SO to form Ph(2)SO(2) was, however, observed only in the DCA-induced photooxygenation of Bu(2)S, in line with the singlet oxygen mechanism suggested for this reaction. No detectable amounts of Ph(2)SO(2) were formed in the ET photooxygenations of PhSMe with both DCA and NMQ(+) and of Bu(s)S with NMQ(+). This finding, coupled with the observation that (1)O(2) and ET photooxygenations lead to different product distributions, makes it unlikely that, as currently believed, the two processes involve the same intermediate, i.e., a nucleophilic persulfoxide. Furthermore, the cooxidation of Ph(2)SO observed in the DCA-induced photooxygenation of Bu(2)S was drastically reduced when the reaction was performed in the presence of 0.5 M biphenyl as a cosensitizer, that is, under conditions where an (indirect) ET mechanism should operate. This observation confirms that a persulfoxide is formed in singlet oxygen but not in ET photosulfoxidations. The latter conclusion was further supported by the observation that also the intermediate formed in the reaction of thianthrene radical cation with KO(2), a reaction which mimics step d (Scheme 2) in the ET mechanism of photooxygenation, is an electrophilic species, being able to oxidize Ph(2)S but not Ph(2)SO. It is thus proposed that the intermediate involved in ET sulfoxidations is a thiadioxirane, whose properties (it is an electrophilic species) seem more in line with the observed chemistry. Theoretical calculations concerning the reaction of a sulfide radical cation with O(2)(-.) provide a rationale for this proposal.

Electron Transfer and Singlet Oxygen Mechanisms in the Photooxygenation of Dibutyl Sulfide and Thioanisole in MeCN Sensitized by N-Methylquinolinium Tetrafluoborate and 9,10-Dicyanoanthracene. The Probable Involvement of a Thiadioxirane Intermediate in Electron Transfer Photooxygenations / Baciocchi, Enrico; DEL GIACCO, T; Elisei, F; Gerini, Maria Francesca; Guerra, M; Lapi, Andrea; Liberali, P.. - In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY. - ISSN 0002-7863. - STAMPA. - 125:(2003), pp. 16444-16454. [10.1021/ja037591o]

Electron Transfer and Singlet Oxygen Mechanisms in the Photooxygenation of Dibutyl Sulfide and Thioanisole in MeCN Sensitized by N-Methylquinolinium Tetrafluoborate and 9,10-Dicyanoanthracene. The Probable Involvement of a Thiadioxirane Intermediate in Electron Transfer Photooxygenations.

BACIOCCHI, Enrico;GERINI, Maria Francesca;LAPI, Andrea;
2003

Abstract

Photooxygenations of PhSMe and Bu(2)S sensitized by N-methylquinolinium (NMQ(+)) and 9,10-dicyano-anthracene (DCA) in O(2)-saturated MeCN have been investigated by laser and steady-state photolysis. Laser photolysis experiments showed that excited NMQ(+) promotes the efficient formation of sulfide radical cations with both substrates either in the presence or in absence of a cosensitizer (toluene). In contrast, excited DCA promotes the formation of radical ions with PhSMe, but not with Bu(2)S. To observe radical ions with the latter substrate, the presence of a cosensitizer (biphenyl) was necessary. With Bu(2)S, only the dimeric form of the radical cation, (Bu(2)S)(2)(+.), was observed, while the absorptions of both PhSMe(+.) and (PhSMe)(2)(+.) were present in the PhSMe time-resolved spectra. The decay of the radical cations followed second-order kinetics, which in the presence of O(2), was attributed to the reaction of the radical cation (presumably in the monomeric form) with O(2)(-.) generated in the reaction between NMQ(.) or DCA(-.) and O(2). The fluorescence quenching of both NMQ(+) and DCA was also investigated, and it was found that the fluorescence of the two sensitizers is efficiently quenched by both sulfides (rates controlled by diffusion) as well by O(2) (k(q) = 5.9 x 10(9) M(-1) s(-1) with NMQ(+) and 6.8 x 10(9) M(-1) s(-1) with DCA). It was also found that quenching of (1)NMQ(*) by O(2) led to the production of (1)O(2) in significant yield (phi(Delta) = 0.86 in O(2)-saturated solutions) as already observed for (1)DCA(*). The steady-state photolysis experiments showed that the NMQ(+)- and DCA-sensitized photooxygenation of PhSMe afford exclusively the corresponding sulfoxide. A different situation holds for Bu(2)S: with NMQ(+), the formation of Bu(2)SO(2) was accompanied by that of small amounts of Bu(2)S(2); with DCA, the formation of Bu(2)SO(2) was also observed. It was conclusively shown that with both sensitizers, the photooxygenations of PhSMe occur by an electron transfer (ET) mechanism, as no sulfoxidation was observed in the presence of benzoquinone (BQ), which is a trap for O(2)(-.) NMQ(.), and DCA(-.). BQ also suppressed the NMQ(+)-sensitized photooxygenation of Bu(2)S, but not that sensitized by DCA, indicating that the former is an ET process, whereas the second proceeds via singlet oxygen. In agreement with the latter conclusion, it was also found that the relative rate of the DCA-induced photooxygenation of Bu(2)S decreases by increasing the initial concentration of the substrate and is slowed by DABCO (an efficient singlet oxygen quencher). To shed light on the actual role of a persulfoxide intermediate also in ET photooxygenations, experiments in the presence of Ph(2)SO (a trap for the persulfoxide) were carried out. Cooxidation of Ph(2)SO to form Ph(2)SO(2) was, however, observed only in the DCA-induced photooxygenation of Bu(2)S, in line with the singlet oxygen mechanism suggested for this reaction. No detectable amounts of Ph(2)SO(2) were formed in the ET photooxygenations of PhSMe with both DCA and NMQ(+) and of Bu(s)S with NMQ(+). This finding, coupled with the observation that (1)O(2) and ET photooxygenations lead to different product distributions, makes it unlikely that, as currently believed, the two processes involve the same intermediate, i.e., a nucleophilic persulfoxide. Furthermore, the cooxidation of Ph(2)SO observed in the DCA-induced photooxygenation of Bu(2)S was drastically reduced when the reaction was performed in the presence of 0.5 M biphenyl as a cosensitizer, that is, under conditions where an (indirect) ET mechanism should operate. This observation confirms that a persulfoxide is formed in singlet oxygen but not in ET photosulfoxidations. The latter conclusion was further supported by the observation that also the intermediate formed in the reaction of thianthrene radical cation with KO(2), a reaction which mimics step d (Scheme 2) in the ET mechanism of photooxygenation, is an electrophilic species, being able to oxidize Ph(2)S but not Ph(2)SO. It is thus proposed that the intermediate involved in ET sulfoxidations is a thiadioxirane, whose properties (it is an electrophilic species) seem more in line with the observed chemistry. Theoretical calculations concerning the reaction of a sulfide radical cation with O(2)(-.) provide a rationale for this proposal.
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Electron Transfer and Singlet Oxygen Mechanisms in the Photooxygenation of Dibutyl Sulfide and Thioanisole in MeCN Sensitized by N-Methylquinolinium Tetrafluoborate and 9,10-Dicyanoanthracene. The Probable Involvement of a Thiadioxirane Intermediate in Electron Transfer Photooxygenations / Baciocchi, Enrico; DEL GIACCO, T; Elisei, F; Gerini, Maria Francesca; Guerra, M; Lapi, Andrea; Liberali, P.. - In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY. - ISSN 0002-7863. - STAMPA. - 125:(2003), pp. 16444-16454. [10.1021/ja037591o]
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11573/145659
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