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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...
Autores principales: | , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Royal Society of Chemistry
2016
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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. |
format | Online Article Text |
id | pubmed-5450590 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2016 |
publisher | Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
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)˙(–)
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title_full | Multi-electron reactivity of a cofacial di-tin(ii) cryptand: partial reduction of sulfur and selenium and reversible generation of S(3)˙(–)
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title_fullStr | Multi-electron reactivity of a cofacial di-tin(ii) cryptand: partial reduction of sulfur and selenium and reversible generation of S(3)˙(–)
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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)˙(–)
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title_short | Multi-electron reactivity of a cofacial di-tin(ii) cryptand: partial reduction of sulfur and selenium and reversible generation of S(3)˙(–)
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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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