Multi-electron reactivity of a cofacial di-tin(I) cryptand: partial reduction of sulfur and selenium and reversible generation of S[subscript 3][superscript ˙−]
Cofacial bimetallic tin(ii) ([Sn[subscript 2](mBDCA-5t)][superscript 2−], 1) and lead(ii) ([Pb[subscript 2](mBDCA-5t)][superscrip 2−], 2) complexes have been prepared by hexadeprotonation of hexacarboxamide cryptand mBDCA-5t-H[subscript 6] together with double Sn(ii) or Pb(ii) insertion. Reaction of...
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| Format: | Article |
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Royal Society of Chemistry (RSC)
2018
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| Online Access: | http://hdl.handle.net/1721.1/113233 https://orcid.org/0000-0001-9783-907X https://orcid.org/0000-0003-2568-3269 |
| _version_ | 1811081877078933504 |
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| author | Dai, Yizhe Wu, Gang Nocera, Daniel G. Stauber, Julia M. Mueller, Peter Cummins, Christopher C |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Dai, Yizhe Wu, Gang Nocera, Daniel G. Stauber, Julia M. Mueller, Peter Cummins, Christopher C |
| author_sort | Dai, Yizhe |
| collection | MIT |
| description | Cofacial bimetallic tin(ii) ([Sn[subscript 2](mBDCA-5t)][superscript 2−], 1) and lead(ii) ([Pb[subscript 2](mBDCA-5t)][superscrip 2−], 2) complexes have been prepared by hexadeprotonation of hexacarboxamide cryptand mBDCA-5t-H[subscript 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[subscript 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[subscript 5])Sn[subscript 2](μ-S)(mBDCA-5t)][superscript 2−] (4) indicate that the complex acts reversibly as a source of S[subscript 3][superscript −] in DMF solution with a K[subscript eq] = 0.012 ± 0.002. Reductive removal of all six chalcogen atoms is achieved through treatment of [(μ-E[subscript 5])Sn[subscript 2](μ-E)(mBDCA-5t)][superscript 2−] with PR[subscript 3] (R =[superscript t]Bu, Ph, O[superscript i] Pr) to produce six equiv. of the corresponding EPR[subscript 3] compound with regeneration of di-tin(ii) cryptand complex 1. |
| first_indexed | 2024-09-23T11:53:49Z |
| format | Article |
| id | mit-1721.1/113233 |
| institution | Massachusetts Institute of Technology |
| last_indexed | 2024-09-23T11:53:49Z |
| publishDate | 2018 |
| publisher | Royal Society of Chemistry (RSC) |
| record_format | dspace |
| spelling | mit-1721.1/1132332022-09-27T22:40:42Z Multi-electron reactivity of a cofacial di-tin(I) cryptand: partial reduction of sulfur and selenium and reversible generation of S[subscript 3][superscript ˙−] Dai, Yizhe Wu, Gang Nocera, Daniel G. Stauber, Julia M. Mueller, Peter Cummins, Christopher C Massachusetts Institute of Technology. Department of Chemistry Stauber, Julia M. Mueller, Peter Cummins, Christopher C Cofacial bimetallic tin(ii) ([Sn[subscript 2](mBDCA-5t)][superscript 2−], 1) and lead(ii) ([Pb[subscript 2](mBDCA-5t)][superscrip 2−], 2) complexes have been prepared by hexadeprotonation of hexacarboxamide cryptand mBDCA-5t-H[subscript 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[subscript 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[subscript 5])Sn[subscript 2](μ-S)(mBDCA-5t)][superscript 2−] (4) indicate that the complex acts reversibly as a source of S[subscript 3][superscript −] in DMF solution with a K[subscript eq] = 0.012 ± 0.002. Reductive removal of all six chalcogen atoms is achieved through treatment of [(μ-E[subscript 5])Sn[subscript 2](μ-E)(mBDCA-5t)][superscript 2−] with PR[subscript 3] (R =[superscript t]Bu, Ph, O[superscript i] Pr) to produce six equiv. of the corresponding EPR[subscript 3] compound with regeneration of di-tin(ii) cryptand complex 1. National Science Foundation (U.S.) (CHE1305124) 2018-01-19T15:29:02Z 2018-01-19T15:29:02Z 2016-07 2016-04 2018-01-18T19:14:57Z Article http://purl.org/eprint/type/JournalArticle 2041-6520 2041-6539 http://hdl.handle.net/1721.1/113233 Stauber, Julia M., et al. “Multi-Electron Reactivity of a Cofacial Di-Tin( ii ) Cryptand: Partial Reduction of Sulfur and Selenium and Reversible Generation of S[subscript 3][superscript ˙ −].” Chemical Science, vol. 7, no. 12, 2016, pp. 6928–33. https://orcid.org/0000-0001-9783-907X https://orcid.org/0000-0003-2568-3269 http://dx.doi.org/10.1039/C6SC01754A Chemical Science Creative Commons Attribution 3.0 Unported license http://creativecommons.org/licenses/by/3.0/ application/pdf Royal Society of Chemistry (RSC) Royal Society of Chemistry |
| spellingShingle | Dai, Yizhe Wu, Gang Nocera, Daniel G. Stauber, Julia M. Mueller, Peter Cummins, Christopher C Multi-electron reactivity of a cofacial di-tin(I) cryptand: partial reduction of sulfur and selenium and reversible generation of S[subscript 3][superscript ˙−] |
| title | Multi-electron reactivity of a cofacial di-tin(I) cryptand: partial reduction of sulfur and selenium and reversible generation of S[subscript 3][superscript ˙−] |
| title_full | Multi-electron reactivity of a cofacial di-tin(I) cryptand: partial reduction of sulfur and selenium and reversible generation of S[subscript 3][superscript ˙−] |
| title_fullStr | Multi-electron reactivity of a cofacial di-tin(I) cryptand: partial reduction of sulfur and selenium and reversible generation of S[subscript 3][superscript ˙−] |
| title_full_unstemmed | Multi-electron reactivity of a cofacial di-tin(I) cryptand: partial reduction of sulfur and selenium and reversible generation of S[subscript 3][superscript ˙−] |
| title_short | Multi-electron reactivity of a cofacial di-tin(I) cryptand: partial reduction of sulfur and selenium and reversible generation of S[subscript 3][superscript ˙−] |
| title_sort | multi electron reactivity of a cofacial di tin i cryptand partial reduction of sulfur and selenium and reversible generation of s subscript 3 superscript ˙ |
| url | http://hdl.handle.net/1721.1/113233 https://orcid.org/0000-0001-9783-907X https://orcid.org/0000-0003-2568-3269 |
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