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Multi-electron reactivity of a cofacial di-tin(ii) cryptand: partial reduction of sulfur and selenium and reversible generation of S(3)˙(–)

Cofacial bimetallic tin(ii) ([Sn(2)(mBDCA-5t)](2–), 1) and lead(ii) ([Pb(2)(mBDCA-5t)](2–), 2) complexes have been prepared by hexadeprotonation of hexacarboxamide cryptand mBDCA-5t-H(6) together with double Sn(ii) or Pb(ii) insertion. Reaction of 1 with elemental sulfur or selenium generates di-tin...

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Autores principales: Stauber, Julia M., Müller, Peter, Dai, Yizhe, Wu, Gang, Nocera, Daniel G., Cummins, Christopher C.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Royal Society of Chemistry 2016
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5450590/
https://www.ncbi.nlm.nih.gov/pubmed/28567264
http://dx.doi.org/10.1039/c6sc01754a
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author Stauber, Julia M.
Müller, Peter
Dai, Yizhe
Wu, Gang
Nocera, Daniel G.
Cummins, Christopher C.
author_facet Stauber, Julia M.
Müller, Peter
Dai, Yizhe
Wu, Gang
Nocera, Daniel G.
Cummins, Christopher C.
author_sort Stauber, Julia M.
collection PubMed
description Cofacial bimetallic tin(ii) ([Sn(2)(mBDCA-5t)](2–), 1) and lead(ii) ([Pb(2)(mBDCA-5t)](2–), 2) complexes have been prepared by hexadeprotonation of hexacarboxamide cryptand mBDCA-5t-H(6) 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-E(5) 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-S(5))Sn(2)(μ-S)(mBDCA-5t)](2–) (4) indicate that the complex acts reversibly as a source of S(3)˙(–) in DMF solution with a K (eq) = 0.012 ± 0.002. Reductive removal of all six chalcogen atoms is achieved through treatment of [(μ-E(5))Sn(2)(μ-E)(mBDCA-5t)](2–) with PR(3) (R = ( 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.
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spelling pubmed-54505902017-05-31 Multi-electron reactivity of a cofacial di-tin(ii) cryptand: partial reduction of sulfur and selenium and reversible generation of S(3)˙(–) Stauber, Julia M. Müller, Peter Dai, Yizhe Wu, Gang Nocera, Daniel G. Cummins, Christopher C. Chem Sci Chemistry Cofacial bimetallic tin(ii) ([Sn(2)(mBDCA-5t)](2–), 1) and lead(ii) ([Pb(2)(mBDCA-5t)](2–), 2) complexes have been prepared by hexadeprotonation of hexacarboxamide cryptand mBDCA-5t-H(6) 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-E(5) 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-S(5))Sn(2)(μ-S)(mBDCA-5t)](2–) (4) indicate that the complex acts reversibly as a source of S(3)˙(–) in DMF solution with a K (eq) = 0.012 ± 0.002. Reductive removal of all six chalcogen atoms is achieved through treatment of [(μ-E(5))Sn(2)(μ-E)(mBDCA-5t)](2–) with PR(3) (R = ( 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. Royal Society of Chemistry 2016-12-01 2016-07-06 /pmc/articles/PMC5450590/ /pubmed/28567264 http://dx.doi.org/10.1039/c6sc01754a Text en This journal is © The Royal Society of Chemistry 2016 https://creativecommons.org/licenses/by/3.0/This is an Open Access article distributed under the terms of the Creative Commons Attribution 3.0 Unported License (http://creativecommons.org/licenses/by/3.0/ (https://creativecommons.org/licenses/by/3.0/) ) which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
spellingShingle Chemistry
Stauber, Julia M.
Müller, Peter
Dai, Yizhe
Wu, Gang
Nocera, Daniel G.
Cummins, Christopher C.
Multi-electron reactivity of a cofacial di-tin(ii) cryptand: partial reduction of sulfur and selenium and reversible generation of S(3)˙(–)
title Multi-electron reactivity of a cofacial di-tin(ii) cryptand: partial reduction of sulfur and selenium and reversible generation of S(3)˙(–)
title_full Multi-electron reactivity of a cofacial di-tin(ii) cryptand: partial reduction of sulfur and selenium and reversible generation of S(3)˙(–)
title_fullStr Multi-electron reactivity of a cofacial di-tin(ii) cryptand: partial reduction of sulfur and selenium and reversible generation of S(3)˙(–)
title_full_unstemmed Multi-electron reactivity of a cofacial di-tin(ii) cryptand: partial reduction of sulfur and selenium and reversible generation of S(3)˙(–)
title_short Multi-electron reactivity of a cofacial di-tin(ii) cryptand: partial reduction of sulfur and selenium and reversible generation of S(3)˙(–)
title_sort multi-electron reactivity of a cofacial di-tin(ii) cryptand: partial reduction of sulfur and selenium and reversible generation of s(3)˙(–)
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5450590/
https://www.ncbi.nlm.nih.gov/pubmed/28567264
http://dx.doi.org/10.1039/c6sc01754a
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