In Situ Reaction Monitoring Reveals a Diastereoselective Ligand Exchange Reaction between the Intrinsically Chiral Au38(SR)24 and Chiral Thiols
The ligand exchange reaction between racemic Au38(2-PET)24 (2-PET = 2-phenylethylthiolate) clusters and enantiopure 1,1′-binaphthyl-2,2′-dithiol (BINAS) was monitored in situ using a chiral high-performance liquid chromatography approach. In the first exchange step, a clear preference of R-BINAS for...
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| Published in | Journal of the American Chemical Society Vol. 134; no. 50; pp. 20302 - 20305 |
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| Main Authors | , , , |
| Format | Journal Article |
| Language | English |
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United States
American Chemical Society
19.12.2012
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| Abstract | The ligand exchange reaction between racemic Au38(2-PET)24 (2-PET = 2-phenylethylthiolate) clusters and enantiopure 1,1′-binaphthyl-2,2′-dithiol (BINAS) was monitored in situ using a chiral high-performance liquid chromatography approach. In the first exchange step, a clear preference of R-BINAS for the left-handed enantiomer of Au38(2-PET)24 is observed (about 4 times faster than reaction with the right-handed enantiomer). The second exchange step is much slower than the first step. BINAS substitution deactivates the cluster for further exchange, which is attributed to (stereo)electronic effects. The results constitute the first example of a ligand exchange reaction in a thiolate-protected gold cluster with directed enrichment of a defined species in the product mixture. This may open new possibilities for the design of nanomaterials with tailored properties. |
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| AbstractList | The ligand exchange reaction between racemic Au(38)(2-PET)(24) (2-PET = 2-phenylethylthiolate) clusters and enantiopure 1,1'-binaphthyl-2,2'-dithiol (BINAS) was monitored in situ using a chiral high-performance liquid chromatography approach. In the first exchange step, a clear preference of R-BINAS for the left-handed enantiomer of Au(38)(2-PET)(24) is observed (about 4 times faster than reaction with the right-handed enantiomer). The second exchange step is much slower than the first step. BINAS substitution deactivates the cluster for further exchange, which is attributed to (stereo)electronic effects. The results constitute the first example of a ligand exchange reaction in a thiolate-protected gold cluster with directed enrichment of a defined species in the product mixture. This may open new possibilities for the design of nanomaterials with tailored properties.The ligand exchange reaction between racemic Au(38)(2-PET)(24) (2-PET = 2-phenylethylthiolate) clusters and enantiopure 1,1'-binaphthyl-2,2'-dithiol (BINAS) was monitored in situ using a chiral high-performance liquid chromatography approach. In the first exchange step, a clear preference of R-BINAS for the left-handed enantiomer of Au(38)(2-PET)(24) is observed (about 4 times faster than reaction with the right-handed enantiomer). The second exchange step is much slower than the first step. BINAS substitution deactivates the cluster for further exchange, which is attributed to (stereo)electronic effects. The results constitute the first example of a ligand exchange reaction in a thiolate-protected gold cluster with directed enrichment of a defined species in the product mixture. This may open new possibilities for the design of nanomaterials with tailored properties. The ligand exchange reaction between racemic Au38(2-PET)24 (2-PET = 2-phenylethylthiolate) clusters and enantiopure 1,1′-binaphthyl-2,2′-dithiol (BINAS) was monitored in situ using a chiral high-performance liquid chromatography approach. In the first exchange step, a clear preference of R-BINAS for the left-handed enantiomer of Au38(2-PET)24 is observed (about 4 times faster than reaction with the right-handed enantiomer). The second exchange step is much slower than the first step. BINAS substitution deactivates the cluster for further exchange, which is attributed to (stereo)electronic effects. The results constitute the first example of a ligand exchange reaction in a thiolate-protected gold cluster with directed enrichment of a defined species in the product mixture. This may open new possibilities for the design of nanomaterials with tailored properties. The ligand exchange reaction between racemic Au₃₈(2-PET)₂₄ (2-PET = 2-phenylethylthiolate) clusters and enantiopure 1,1′-binaphthyl-2,2′-dithiol (BINAS) was monitored in situ using a chiral high-performance liquid chromatography approach. In the first exchange step, a clear preference of R-BINAS for the left-handed enantiomer of Au₃₈(2-PET)₂₄ is observed (about 4 times faster than reaction with the right-handed enantiomer). The second exchange step is much slower than the first step. BINAS substitution deactivates the cluster for further exchange, which is attributed to (stereo)electronic effects. The results constitute the first example of a ligand exchange reaction in a thiolate-protected gold cluster with directed enrichment of a defined species in the product mixture. This may open new possibilities for the design of nanomaterials with tailored properties. The ligand exchange reaction between racemic Au(38)(2-PET)(24) (2-PET = 2-phenylethylthiolate) clusters and enantiopure 1,1'-binaphthyl-2,2'-dithiol (BINAS) was monitored in situ using a chiral high-performance liquid chromatography approach. In the first exchange step, a clear preference of R-BINAS for the left-handed enantiomer of Au(38)(2-PET)(24) is observed (about 4 times faster than reaction with the right-handed enantiomer). The second exchange step is much slower than the first step. BINAS substitution deactivates the cluster for further exchange, which is attributed to (stereo)electronic effects. The results constitute the first example of a ligand exchange reaction in a thiolate-protected gold cluster with directed enrichment of a defined species in the product mixture. This may open new possibilities for the design of nanomaterials with tailored properties. |
| Author | Knoppe, Stefan Azoulay, Raymond Dass, Amala Bürgi, Thomas |
| AuthorAffiliation | University of Mississippi University of Geneva |
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| BackLink | https://www.ncbi.nlm.nih.gov/pubmed/23215037$$D View this record in MEDLINE/PubMed |
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| Snippet | The ligand exchange reaction between racemic Au38(2-PET)24 (2-PET = 2-phenylethylthiolate) clusters and enantiopure 1,1′-binaphthyl-2,2′-dithiol (BINAS) was... The ligand exchange reaction between racemic Au(38)(2-PET)(24) (2-PET = 2-phenylethylthiolate) clusters and enantiopure 1,1'-binaphthyl-2,2'-dithiol (BINAS)... The ligand exchange reaction between racemic Au₃₈(2-PET)₂₄ (2-PET = 2-phenylethylthiolate) clusters and enantiopure 1,1′-binaphthyl-2,2′-dithiol (BINAS) was... |
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| SubjectTerms | enantiomers gold high performance liquid chromatography ligands monitoring nanomaterials thiols |
| Title | In Situ Reaction Monitoring Reveals a Diastereoselective Ligand Exchange Reaction between the Intrinsically Chiral Au38(SR)24 and Chiral Thiols |
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