Issue 12, 2016

Multi-electron reactivity of a cofacial di-tin(ii) cryptand: partial reduction of sulfur and selenium and reversible generation of S3˙

Abstract

Cofacial bimetallic tin(II) ([Sn2(mBDCA-5t)]2−, 1) and lead(II) ([Pb2(mBDCA-5t)]2−, 2) complexes have been prepared by hexadeprotonation of hexacarboxamide cryptand mBDCA-5t-H6 together with double Sn(II) or Pb(II) insertion. Reaction of 1 with elemental sulfur or selenium generates di-tin polychalcogenide complexes containing μ-E and bridging μ-E5 ligands where E = S or Se, and the Sn(II) centers have both been oxidized to Sn(IV). Solution and solid-state UV-Vis spectra of [(μ-S5)Sn2(μ-S)(mBDCA-5t)]2− (4) indicate that the complex acts reversibly as a source of S3˙ in DMF solution with a Keq = 0.012 ± 0.002. Reductive removal of all six chalcogen atoms is achieved through treatment of [(μ-E5)Sn2(μ-E)(mBDCA-5t)]2− with PR3 (R = tBu, Ph, OiPr) to produce six equiv. of the corresponding EPR3 compound with regeneration of di-tin(II) cryptand complex 1.

Graphical abstract: Multi-electron reactivity of a cofacial di-tin(ii) cryptand: partial reduction of sulfur and selenium and reversible generation of S3˙−

Supplementary files

Article information

Article type
Edge Article
Submitted
21 4 2016
Accepted
04 7 2016
First published
06 7 2016
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2016,7, 6928-6933

Multi-electron reactivity of a cofacial di-tin(II) cryptand: partial reduction of sulfur and selenium and reversible generation of S3˙

J. M. Stauber, P. Müller, Y. Dai, G. Wu, D. G. Nocera and C. C. Cummins, Chem. Sci., 2016, 7, 6928 DOI: 10.1039/C6SC01754A

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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