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月 2016
Accepted
04 7月 2016
First published
06 7月 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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