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Reactions of Organic Disulfides and Gold(I) Complexes
Gold-thiolate/disulfide exchange reactions of (p-SC(6)H(4)Cl)(2) with Ph(3)PAu(SC(6)H(4)CH(3)), dppm(AuSC(6)H(4)CH(3))(2), and dppe(AuSC(6)H(4)CH(3)) (2) were investigated. The rate of reactivity of the gold-thiolate complexes with (p-SC(6)H(4)Cl)(2) is: dppm(AuSC(6)H(4)CH(3))(2)>> dppe(AuSC(6...
Autores principales: | , , , , , |
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Formato: | Texto |
Lenguaje: | English |
Publicado: |
Hindawi Publishing Corporation
1999
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC2365179/ https://www.ncbi.nlm.nih.gov/pubmed/18475899 http://dx.doi.org/10.1155/MBD.1999.247 |
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author | DiLorenzo, Melanie Ganesh, Shantheni Tadayon, Lily Chen, Jinhua Bruce, Mitchell R. M. Bruce, Alice E. |
author_facet | DiLorenzo, Melanie Ganesh, Shantheni Tadayon, Lily Chen, Jinhua Bruce, Mitchell R. M. Bruce, Alice E. |
author_sort | DiLorenzo, Melanie |
collection | PubMed |
description | Gold-thiolate/disulfide exchange reactions of (p-SC(6)H(4)Cl)(2) with Ph(3)PAu(SC(6)H(4)CH(3)), dppm(AuSC(6)H(4)CH(3))(2), and dppe(AuSC(6)H(4)CH(3)) (2) were investigated. The rate of reactivity of the gold-thiolate complexes with (p-SC(6)H(4)Cl)(2) is: dppm(AuSC(6)H(4)CH(3))(2)>> dppe(AuSC(6)H(4)CH(3))(2)>Ph(2)PAu (SC(6)H(4)CH(3)). This order correlates with conductivity measurements and two ionic mechanisms have been evaluated. (1)H NMR experiments demonstrate that in the reaction of dppm(AuSC(6)H(4)CH(3))(2) with (p-SC(6)H(4)Cl)(2), the mixed disulfide, ClC(6)H(4)SSC(6)H(4)CH(3), forms first, followed by the formation of (p-SC(6)H(4)CH(3))(2). The rate law is first order in (pp-SC(6)H (4)Cl)(2) and partial order in dppm(AuSC(6)H(4)CH(3))(2). Results from electrochemical and chemical reactivity studies suggest that free thiolate is not involved in the gold-thiolate/disulfide exchange reaction. A more likely source of ions is the dissociation of a proton from the methylene backbone of the dppm ligand which has been shown to exchange with D(2)O. The implications of this are discussed in terms of a possible mechanism for the gold-thiolate/disulfide exchange reaction. |
format | Text |
id | pubmed-2365179 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 1999 |
publisher | Hindawi Publishing Corporation |
record_format | MEDLINE/PubMed |
spelling | pubmed-23651792008-05-12 Reactions of Organic Disulfides and Gold(I) Complexes DiLorenzo, Melanie Ganesh, Shantheni Tadayon, Lily Chen, Jinhua Bruce, Mitchell R. M. Bruce, Alice E. Met Based Drugs Research Article Gold-thiolate/disulfide exchange reactions of (p-SC(6)H(4)Cl)(2) with Ph(3)PAu(SC(6)H(4)CH(3)), dppm(AuSC(6)H(4)CH(3))(2), and dppe(AuSC(6)H(4)CH(3)) (2) were investigated. The rate of reactivity of the gold-thiolate complexes with (p-SC(6)H(4)Cl)(2) is: dppm(AuSC(6)H(4)CH(3))(2)>> dppe(AuSC(6)H(4)CH(3))(2)>Ph(2)PAu (SC(6)H(4)CH(3)). This order correlates with conductivity measurements and two ionic mechanisms have been evaluated. (1)H NMR experiments demonstrate that in the reaction of dppm(AuSC(6)H(4)CH(3))(2) with (p-SC(6)H(4)Cl)(2), the mixed disulfide, ClC(6)H(4)SSC(6)H(4)CH(3), forms first, followed by the formation of (p-SC(6)H(4)CH(3))(2). The rate law is first order in (pp-SC(6)H (4)Cl)(2) and partial order in dppm(AuSC(6)H(4)CH(3))(2). Results from electrochemical and chemical reactivity studies suggest that free thiolate is not involved in the gold-thiolate/disulfide exchange reaction. A more likely source of ions is the dissociation of a proton from the methylene backbone of the dppm ligand which has been shown to exchange with D(2)O. The implications of this are discussed in terms of a possible mechanism for the gold-thiolate/disulfide exchange reaction. Hindawi Publishing Corporation 1999 /pmc/articles/PMC2365179/ /pubmed/18475899 http://dx.doi.org/10.1155/MBD.1999.247 Text en Copyright © 1999 Hindawi Publishing Corporation. http://creativecommons.org/licenses/by/ This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. |
spellingShingle | Research Article DiLorenzo, Melanie Ganesh, Shantheni Tadayon, Lily Chen, Jinhua Bruce, Mitchell R. M. Bruce, Alice E. Reactions of Organic Disulfides and Gold(I) Complexes |
title | Reactions of Organic Disulfides and Gold(I) Complexes |
title_full | Reactions of Organic Disulfides and Gold(I) Complexes |
title_fullStr | Reactions of Organic Disulfides and Gold(I) Complexes |
title_full_unstemmed | Reactions of Organic Disulfides and Gold(I) Complexes |
title_short | Reactions of Organic Disulfides and Gold(I) Complexes |
title_sort | reactions of organic disulfides and gold(i) complexes |
topic | Research Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC2365179/ https://www.ncbi.nlm.nih.gov/pubmed/18475899 http://dx.doi.org/10.1155/MBD.1999.247 |
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