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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Author(s)
Dai, Yizhe
Wu, Gang
Cummins, Christopher C.
Stauber, Julia M.
Miller, Peter G
Nocera, Daniel G.
Date Issued
July 2016
Journal
Chemical Science
Publisher
Royal Society of Chemistry
Citation
Stauber, Julia M., Peter Müller, Yizhe Dai, Gang Wu, Daniel G. Nocera, and Christopher C. Cummins. “Multi-Electron Reactivity of a Cofacial Di-Tin(ii) Cryptand: Partial Reduction of Sulfur and Selenium and Reversible Generation of S3˙−.” Chem. Sci. 7, no. 12 (2016): 6928–6933.
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Final published version
Abstract
Cofacial bimetallic tin( II ) ([Sn 2 ( m BDCA-5t)] 2-, 1) and lead( II ) ([Pb₂(mBDCA-5t)]²-, 2) complexes have been prepared by hexadeprotonation of hexacarboxamide cryptand m BDCA-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 m -E and bridging m -E 5 ligands where E ¼ S or Se, and the Sn( II ) centers have both been oxidized to Sn( IV ). Solution and solid-state UV-Vis spectra of [( m -S 5 )Sn 2 ( m -S)( m BDCA-5t)] 2 ( 4 ) indicate that the complex acts reversibly as a source of S 3 c in DMF solution with a K eq ¼ 0.012 0.002. Reductive removal of all six chalcogen atoms is achieved through treatment of [( m -E 5 )Sn 2 ( m -E)( m BDCA- 5t)] 2 with PR 3 (R ¼ t Bu, Ph, O i Pr) to produce six equiv. of the corresponding EPR 3 compound with regeneration of di-tin( II ) cryptand complex 1.
MIT Department
Massachusetts Institute of Technology. Institute for Medical Engineering & Science
Massachusetts Institute of Technology. Department of Biology
Massachusetts Institute of Technology. Department of Chemical Engineering
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1039/c6sc01754a
