Tripodal Tris-tacn and Tris-DPA Platforms for Assembling Phosphate-Templated Trimetallic Centers
Multidentate tripodal ligands, N(CH2-m-C6H4-CH2tacn)3 (L1) and N(CH2-o-C6H4-CH2N(CH2py)2)3 (L2), have been devised for assembling high-nuclearity metal clusters. By using the same tripodal platform with different ligand appendages, either triazacyclononanes or dipicolylamines, and functionalizing ei...
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| Format: | Article |
| Language: | en_US |
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American Chemical Society
2011
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| Online Access: | http://hdl.handle.net/1721.1/67821 https://orcid.org/0000-0002-2693-4982 |
| _version_ | 1826218046537072640 |
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| author | Cao, Rui Mueller, Peter Lippard, Stephen J. |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Cao, Rui Mueller, Peter Lippard, Stephen J. |
| author_sort | Cao, Rui |
| collection | MIT |
| description | Multidentate tripodal ligands, N(CH2-m-C6H4-CH2tacn)3 (L1) and N(CH2-o-C6H4-CH2N(CH2py)2)3 (L2), have been devised for assembling high-nuclearity metal clusters. By using the same tripodal platform with different ligand appendages, either triazacyclononanes or dipicolylamines, and functionalizing either the ortho or the meta positions on the tris(xylyl) linker arms, discrete trimetal phosphate units of relevance to phosphate-metabolizing trimetallic centers in biology were prepared. Four such compounds, [(CuIICl)3(HPO4)L1](PF6) (1), [(CuIICl)3(HAsO4)L1](PF6) (2), Na2[MnIII6MnII2(H2O)2(HPO4)6(PO4)4(L1)2] (3), and [CoII3(H2PO4)Cl2(MeCN)L2](PF6)3 (4), all containing three metal centers bound to a central phosphate or arsenate unit bridging oxygen atoms, have been synthesized and structurally characterized. These results demonstrate the propensity of this novel tripodal ligand platform, in the presence of phosphate or arsenate, to assemble {M3(EO4)} units and thus structurally mimic trimetallic active sites of proteins involved in phosphate metabolism. Reactivity studies reveal that the tricopper complex 1 is more efficient than monocopper analogues in catalyzing the hydrolysis of 4-nitrophenyl phosphate. |
| first_indexed | 2024-09-23T17:13:18Z |
| format | Article |
| id | mit-1721.1/67821 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T17:13:18Z |
| publishDate | 2011 |
| publisher | American Chemical Society |
| record_format | dspace |
| spelling | mit-1721.1/678212022-10-03T11:12:54Z Tripodal Tris-tacn and Tris-DPA Platforms for Assembling Phosphate-Templated Trimetallic Centers Cao, Rui Mueller, Peter Lippard, Stephen J. Massachusetts Institute of Technology. Department of Chemistry Lippard, Stephen J. Lippard, Stephen J. Mueller, Peter Cao, Rui Multidentate tripodal ligands, N(CH2-m-C6H4-CH2tacn)3 (L1) and N(CH2-o-C6H4-CH2N(CH2py)2)3 (L2), have been devised for assembling high-nuclearity metal clusters. By using the same tripodal platform with different ligand appendages, either triazacyclononanes or dipicolylamines, and functionalizing either the ortho or the meta positions on the tris(xylyl) linker arms, discrete trimetal phosphate units of relevance to phosphate-metabolizing trimetallic centers in biology were prepared. Four such compounds, [(CuIICl)3(HPO4)L1](PF6) (1), [(CuIICl)3(HAsO4)L1](PF6) (2), Na2[MnIII6MnII2(H2O)2(HPO4)6(PO4)4(L1)2] (3), and [CoII3(H2PO4)Cl2(MeCN)L2](PF6)3 (4), all containing three metal centers bound to a central phosphate or arsenate unit bridging oxygen atoms, have been synthesized and structurally characterized. These results demonstrate the propensity of this novel tripodal ligand platform, in the presence of phosphate or arsenate, to assemble {M3(EO4)} units and thus structurally mimic trimetallic active sites of proteins involved in phosphate metabolism. Reactivity studies reveal that the tricopper complex 1 is more efficient than monocopper analogues in catalyzing the hydrolysis of 4-nitrophenyl phosphate. Henry & Camille Dreyfus Foundation 2011-12-19T20:39:22Z 2011-12-19T20:39:22Z 2010-11 2011-09 Article http://purl.org/eprint/type/JournalArticle 0002-7863 1520-5126 http://hdl.handle.net/1721.1/67821 Cao, Rui, Peter Müller, and Stephen J. Lippard. “Tripodal Tris-tacn and Tris-dpa Platforms for Assembling Phosphate-Templated Trimetallic Centers.” Journal of the American Chemical Society 132.49 (2010): 17366-17369. https://orcid.org/0000-0002-2693-4982 en_US http://dx.doi.org/10.1021/ja108212v Journal of the American Chemical Society Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. application/pdf American Chemical Society Prof. Lippard via Erja Kajosalo |
| spellingShingle | Cao, Rui Mueller, Peter Lippard, Stephen J. Tripodal Tris-tacn and Tris-DPA Platforms for Assembling Phosphate-Templated Trimetallic Centers |
| title | Tripodal Tris-tacn and Tris-DPA Platforms for Assembling Phosphate-Templated Trimetallic Centers |
| title_full | Tripodal Tris-tacn and Tris-DPA Platforms for Assembling Phosphate-Templated Trimetallic Centers |
| title_fullStr | Tripodal Tris-tacn and Tris-DPA Platforms for Assembling Phosphate-Templated Trimetallic Centers |
| title_full_unstemmed | Tripodal Tris-tacn and Tris-DPA Platforms for Assembling Phosphate-Templated Trimetallic Centers |
| title_short | Tripodal Tris-tacn and Tris-DPA Platforms for Assembling Phosphate-Templated Trimetallic Centers |
| title_sort | tripodal tris tacn and tris dpa platforms for assembling phosphate templated trimetallic centers |
| url | http://hdl.handle.net/1721.1/67821 https://orcid.org/0000-0002-2693-4982 |
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