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Issue 12, 2016
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Multi-electron reactivity of a cofacial di-tin(II) cryptand: partial reduction of sulfur and selenium and reversible generation of S3˙

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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˙−

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Publication details

The article was received on 21 Apr 2016, accepted on 04 Jul 2016 and first published on 06 Jul 2016


Article type: Edge Article
DOI: 10.1039/C6SC01754A
Citation: Chem. Sci., 2016,7, 6928-6933
  • Open access: Creative Commons BY license
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    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

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