Protection against peroxynitrite-mediated nitration reaction by intramolecularly coordinated diorganoselenides

Kumar, Sangit ; Singh, Harkesh B. ; Wolmershäuser, Gotthelf (2006) Protection against peroxynitrite-mediated nitration reaction by intramolecularly coordinated diorganoselenides Organometallics, 25 (2). pp. 382-393. ISSN 0276-7333

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Official URL: http://pubs.acs.org/doi/abs/10.1021/om050353c

Related URL: http://dx.doi.org/10.1021/om050353c

Abstract

A series of intramolecularly Se···X (X=N, O) coordinated diorganoselenides and -sulfides are synthesized by using the heteroatom-directed lithiation route and characterized by multinuclear (1H, 13C, 77Se) NMR, IR spectroscopy, and electrospray mass spectrometry (ES-MS). The intramolecular Se···O interactions in diorganoselenides 26-31 have been studied by multinuclear NMR studies in solution and in the solid state by single-crystal X-ray crystallography. The protection against peroxynitrite-mediated nitration reaction (PN assay) by diorganoselenides/-sulfides (with and without intramolecular coordination) has been evaluated. The PN assay data of diorganoselenides reveal that the selenides 20-22, having a basic amino group (sp3-N donor) in close proximity of selenium, are more active compared to the diorganoselenides 16-19, having an imino group (sp2-N donor), and also show much higher protective action than the unsubstituted diorganoselenides 14 and 15. The diorganoselenides 16-31 were oxidized to corresponding selenoxides 44-59. The redox properties of the selenoxides 13 and 44-59 have been investigated by cyclic voltammetry and potentiometric titration experiments. Two redox potentials for in situ-generated ferrocenyl selenoxides (50, 54-59) were observed. The reduction of selenoxides 13 and 48 to ebselen (2) and selenide 20 with benzenethiol (PhSH) was monitored by ES-MS.

Item Type:Article
Source:Copyright of this article belongs to American Chemical Society.
ID Code:47536
Deposited On:11 Jul 2011 13:43
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