Issue 22, 2017

Heterocyclic bismuth(iii) compounds with transannular N→Bi interactions as catalysts for the oxidation of thiophenol to diphenyldisulfide

Abstract

The reactions between the diorganobismuth(III) bromides [RCH2N(CH2C6H4)2]BiBr [R = C6H5 (1), C6H5CH2 (2)] and appropriate silver salts resulted in new diorganobismuth(III) compounds of the general formula [RCH2N(CH2C6H4)2]BiX [R = C6H5, X = ONO2 (3), OSO2CF3 (4), OSO2C6H4 (CHCH2)-4 (5); R = C6H5CH2, X = ONO2 (6)], based on a butterfly-like tetrahydro-dibenzo[c,f][1,5]azabismocine heterocyclic framework. The new species were structurally characterized in solution by 1H, 13C{H} and 19F{H} NMR and in the solid state by IR spectroscopy and single-crystal X-ray diffraction. The nitrogen atom is intramolecularly coordinated to bismuth, thus resulting in hypercoordinated species of type 12-Bi-5 (3 and 6) and 10-Bi-4 (4 and 5). In addition, compound 4 shows bismuth⋯π arene and compounds 3 and 6 bismuth⋯oxygen intermolecular interactions, thus leading to dimers in the solid state. These compounds were investigated as catalysts for the oxidation of thiophenol to diphenyl disulfide by using air as an oxidizing agent, both in cyclohexane and in an ionic liquid (1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide), at temperatures below 100 °C, affording high reaction rates (TON 34.8, with 100% conversion after 5 h) and a total selectivity to the targeted product.

Graphical abstract: Heterocyclic bismuth(iii) compounds with transannular N→Bi interactions as catalysts for the oxidation of thiophenol to diphenyldisulfide

Supplementary files

Article information

Article type
Paper
Submitted
17 mrt 2017
Accepted
25 mei 2017
First published
26 mei 2017

Catal. Sci. Technol., 2017,7, 5343-5353

Heterocyclic bismuth(III) compounds with transannular N→Bi interactions as catalysts for the oxidation of thiophenol to diphenyldisulfide

A. M. Toma, C. I. Raţ, O. D. Pavel, C. Hardacre, T. Rüffer, H. Lang, M. Mehring, A. Silvestru and V. I. Pârvulescu, Catal. Sci. Technol., 2017, 7, 5343 DOI: 10.1039/C7CY00521K

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements