La Trobe
sathsara_Chal_revise.docx (778.28 kB)
Download file

Diverse reactions of Thiophenes, Selenophenes, and Tellurophenes with strongly oxidizing I(III) PhI(L)2 Reagents

Download (778.28 kB)
We report the outcomes of the reactions of aromatic group 16 thiophene, selenophene, and tellurophene rings with the I(III) oxidants PhI(OAc)(OTf) and [PhI(Pyr) ][OTf] (Pyr = pyridine). In all reactions, oxidative processes take place, with generation of PhI as the reduction product. However, with the exception of tellurophene with PhI(OAc)(OTf), +4 oxidation state complexes are not observed, but rather a variety of other processes occur. In general, where a C-H unit is available on the 5-membered ring, an electrophilic aromatic substitution reaction of either −IPh or pyridine onto the ring occurs. When all positions are blocked, reactions with PhI(OAc)(OTf) give acetic and triflic anhydride as the identifiable oxidative byproducts, while [PhI(Pyr) ][OTf] gives pyridine electrophilic aromatic substitution onto the peripheral rings. Qualitative mechanistic studies indicate that the presence of the oxidizable heteroatom is required for pyridine to act as an electrophile in a substantial manner. 2 2 2 2

Funding

We thank The La Trobe Institute for Molecular Science for their generous funding of this project. This work was also supported by ARC DECRA and Future Fellowships (J.L.D., DE130100186, FT160100007).

History

Publication Date

01/01/2017

Journal

Inorganic Chemistry

Volume

56

Issue

3

Pagination

7p. (p. 1282-1288)

Publisher

American Chemical Society

ISSN

0020-1669

Rights Statement

The Author reserves all moral rights over the deposited text and must be credited if any re-use occurs. Documents deposited in OPAL are the Open Access versions of outputs published elsewhere. Changes resulting from the publishing process may therefore not be reflected in this document. The final published version may be obtained via the publisher’s DOI. Please note that additional copyright and access restrictions may apply to the published version.