Trimethyl phosphite traps intermediates in the reaction of singlet oxygen (1O2) and diethyl sulfide

Nahm, Keepyung; Foote, Christopher S.

doi:10.1021/ja00187a071

Cited by 53 publications

(29 citation statements)

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“…In addition, the trapping agent must be very reactive, allowing it to compete effectively with other reactions of the intermediate. A variety of trapping agents including alcohols [5,6], olefins [7], phosphites [8,9], sulfoxides and sulfides [10], and sulfenate and sulfinate esters [11] have been shown to meet these stringent requirements. Never the less, a need exists for additional trapping agents that exhibit enhanced selectivity for the various peroxidic intermediates and that are stable under a variety of conditions, including biological media.…”

Section: Introductionmentioning

confidence: 99%

Trapping of peroxidic intermediates with sulfur and phosphorus centered electrophiles

Clennan¹,

Stensaas²,

Rupert³

1998

Heteroatom Chem.

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The trapping ability of a new peroxidic trapping agent relative to several well‐established trapping agents was measured. Two different methods for this measurement were utilized. It was shown that adamantylidene adamantane reacts under the trapping conditions to give adamantylidene adamantane epoxide via a more complicated process than previously recognized and is consequently an inappropriate system to make this measurement. In contrast, the use of diethyl sulfide is straightforward and gives reliable values. © 1998 John Wiley & Sons, Inc. Heteroatom Chem 9:51–56, 1998

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Section: Introductionmentioning

confidence: 99%

Trapping of peroxidic intermediates with sulfur and phosphorus centered electrophiles

Clennan¹,

Stensaas²,

Rupert³

1998

Heteroatom Chem.

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“…In addition to the high solvent viscosity, the DMSO solvent may act as a trapping agent of a nucleophilic peroxidic reaction intermediate. 35 Likewise, an electrophilic peroxidic intermediate could have been trapped by dimethyl sulfide (DMS) which may be present as an impurity in the DMSO solvent. In fact, the photoreaction of Pt1 in the CD 3 CN solution was strongly suppressed by the presence of DMS (see Figure S9 of the Supporting Information).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Photoinduced Dimerization Reaction Coupled with Oxygenation of a Platinum(II)–Hydrazone Complex

et al. 2014

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Photoreactivities of Ni(II)- and Pt(II)-hydrazone complexes, [NiCl(L)] (Ni1) and [PtCl(L)] (Pt1), respectively [HL = 2-(diphenylphosphino)benzaldehyde-2-pyridylhydrazone], were investigated in detail via UV-vis absorption, (1)H nuclear magnetic resonance (NMR) spectroscopy, and electrospray ionization time-of-flight (ESI-TOF) mass spectrometry; the two photoproducts obtained from the photoreaction of Pt1 were also successfully identified via X-ray analysis. The absorption bands of the Ni1 and Pt1 complexes were very similar, centered around 530 nm, and were assigned as an intraligand charge transfer transition of the hydrazone moiety. The absorption spectrum of Pt1 in a CH3CN solution changed drastically upon photoirradiation (λ = 530 nm), whereas no change was observed for Ni1. (1)H NMR and ESI-TOF mass spectra under various conditions suggested that the photoexcited Pt1* reacts with dissolved dioxygen to form a reactive intermediate, and the ensuing dark reactions afforded two different products without any decomposition. In contrast to the simple photo-oxidation of HL to form a phosphine oxide HL(P═O), the X-ray crystallographic analyses of the photoproducts clearly indicate the formation of a mononuclear Pt complex with the oxygenated hydrazone ligand (Pt1O) and a dinuclear Pt complex with the oxygenated and dimerized hydrazone ligand (Pt2). The photosensitized reaction in the presence of an (1)O2-generating photosensitizer, methylene blue (MB), also produced Pt1O and Pt2, indicating that the reaction between (1)O2 and ground-state Pt1 is the important step. In a highly viscous dimethyl sulfoxide solution, Pt1 was slowly, but quantitatively, converted to the mononuclear form, Pt1O, without the formation of the dinuclear product, Pt2, upon photoirradiation (and in the reaction photosensitized by MB), suggesting that this photoreaction of Pt1 involves at least one diffusion-controlled reaction. On the other hand, the same complexes Pt1O and Pt2 were also produced in the degassed solution, probably because of the reaction of the photoexcited Pt1* with the biradical character and H2O.

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“…R 1 R 2 S þ is produced by an electron transfer from lone pair electron of sulfur atom of R 1 R 2 S to 1*, and it reacts with O 2 to yield R 1 R 2 SO 2 þ followed by an electron transfer to result in the regeneration of 1 and the formation of R 1 R 2 S þ OO À , which reacts with additional R 1 R 2 S to yield R 1 R 2 SO. 25 Since the initial electron transfer is rate-determining, electronic spin density of the sulfur atom will be the most important factor for photooxidation of diaryl sulfides with O 2 . Thus Mesubstituted (EDG) diphenyl sulfides gave excellent yields, while NO 2 -substituted (EWG) diphenyl sulfides could hardly be oxygenated.…”

Section: Resultsmentioning

confidence: 99%

Selective aerobic oxidation of sulfides to sulfoxides catalyzed by coenzyme NAD+ models

Lin

Wan

et al. 2010

Tetrahedron

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Trimethyl phosphite traps intermediates in the reaction of singlet oxygen (1O2) and diethyl sulfide

Cited by 53 publications

References 0 publications

Trapping of peroxidic intermediates with sulfur and phosphorus centered electrophiles

Trapping of peroxidic intermediates with sulfur and phosphorus centered electrophiles

Photoinduced Dimerization Reaction Coupled with Oxygenation of a Platinum(II)–Hydrazone Complex

Selective aerobic oxidation of sulfides to sulfoxides catalyzed by coenzyme NAD+ models

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