Immobilization, Trapping, and Anion Exchange of Perrhenate Ion Using Copper-Based Tripodal Complexes
We describe a multidentate tripodal ligand in which three pendant arms carrying di(2-picolyl)amine units are linked to the ortho positions of a tris(o-xylyl) scaffold, providing N(CH[subscript 2]-o-C[subscript 6]H[subscript 4]CH[subscript 2]N(CH2py)[subscript 2])[subscript 3] (L). Reaction of L with...
| Main Authors: | , , |
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| Other Authors: | |
| Format: | Article |
| Language: | en_US |
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American Chemical Society (ACS)
2012
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| Online Access: | http://hdl.handle.net/1721.1/74058 https://orcid.org/0000-0002-2693-4982 |
| _version_ | 1811085224185954304 |
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| author | Cao, Rui McCarthy, Brian D. Lippard, Stephen J. |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Cao, Rui McCarthy, Brian D. Lippard, Stephen J. |
| author_sort | Cao, Rui |
| collection | MIT |
| description | We describe a multidentate tripodal ligand in which three pendant arms carrying di(2-picolyl)amine units are linked to the ortho positions of a tris(o-xylyl) scaffold, providing N(CH[subscript 2]-o-C[subscript 6]H[subscript 4]CH[subscript 2]N(CH2py)[subscript 2])[subscript 3] (L). Reaction of L with CuCl[subscript 2] in the presence of hexafluorophosphate anion afforded blue cubes of [(CuCl)[subscript 3]L](PF[subscript 6])[subscript 3]·5H[subscript 2]O (1). Crystallographic studies of 1 revealed that the three symmetry-related arms each coordinate a {Cu[superscript II]Cl} unit, and two molecules of 1 are connected to one another through a Cu(μ-Cl)[subscript 2]Cu bridge, extending the molecular structure to form a two-dimensional (2-D) layer. These 2-D layers pack in an ABCABC... fashion with PF[subscript 6]– anions located in between. Reaction of 1 with a stoichiometric amount of perrhenate ion afforded blue plates of [(CuCl)[subscript 3]L](PF[subscript 6])(ReO[subscript 4])[subscript 2]·3H[subscript 2]O (2). Compound 2 has the same lattice structure as 1, but the tricopper unit backbone now traps one ReO[subscript 4]– anion through Coulombic interactions. In addition, three molecules of 2 are bridged by a perrhenate ion, forming a Cu[subscript 3](μ[superscript 3]-ReO[subscript 4]) cluster, to give a different 2-D structure displaying a rare tridentate bridging ReO[subscript 4]– mode. Thus, in addition to classic perrhenate trapping through weak Coulombic interactions, 2 represents an exceptional example in which the ReO[subscript 4]– anion is immobilized in an extended framework through tight covalent interactions. The interlamellar PF[subscript 6]– anions in 1 can be exchanged with other anions including perrhenate, perchlorate, or periodate. The structural similarity between perrhenate and pertechnetate makes these materials of potential interest for pertechnetate trapping. |
| first_indexed | 2024-09-23T13:05:36Z |
| format | Article |
| id | mit-1721.1/74058 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T13:05:36Z |
| publishDate | 2012 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/740582022-09-28T11:56:50Z Immobilization, Trapping, and Anion Exchange of Perrhenate Ion Using Copper-Based Tripodal Complexes Cao, Rui McCarthy, Brian D. Lippard, Stephen J. Massachusetts Institute of Technology. Department of Chemistry Lippard, Stephen J. Cao, Rui McCarthy, Brian D. Lippard, Stephen J. We describe a multidentate tripodal ligand in which three pendant arms carrying di(2-picolyl)amine units are linked to the ortho positions of a tris(o-xylyl) scaffold, providing N(CH[subscript 2]-o-C[subscript 6]H[subscript 4]CH[subscript 2]N(CH2py)[subscript 2])[subscript 3] (L). Reaction of L with CuCl[subscript 2] in the presence of hexafluorophosphate anion afforded blue cubes of [(CuCl)[subscript 3]L](PF[subscript 6])[subscript 3]·5H[subscript 2]O (1). Crystallographic studies of 1 revealed that the three symmetry-related arms each coordinate a {Cu[superscript II]Cl} unit, and two molecules of 1 are connected to one another through a Cu(μ-Cl)[subscript 2]Cu bridge, extending the molecular structure to form a two-dimensional (2-D) layer. These 2-D layers pack in an ABCABC... fashion with PF[subscript 6]– anions located in between. Reaction of 1 with a stoichiometric amount of perrhenate ion afforded blue plates of [(CuCl)[subscript 3]L](PF[subscript 6])(ReO[subscript 4])[subscript 2]·3H[subscript 2]O (2). Compound 2 has the same lattice structure as 1, but the tricopper unit backbone now traps one ReO[subscript 4]– anion through Coulombic interactions. In addition, three molecules of 2 are bridged by a perrhenate ion, forming a Cu[subscript 3](μ[superscript 3]-ReO[subscript 4]) cluster, to give a different 2-D structure displaying a rare tridentate bridging ReO[subscript 4]– mode. Thus, in addition to classic perrhenate trapping through weak Coulombic interactions, 2 represents an exceptional example in which the ReO[subscript 4]– anion is immobilized in an extended framework through tight covalent interactions. The interlamellar PF[subscript 6]– anions in 1 can be exchanged with other anions including perrhenate, perchlorate, or periodate. The structural similarity between perrhenate and pertechnetate makes these materials of potential interest for pertechnetate trapping. 2012-10-17T19:40:57Z 2012-10-17T19:40:57Z 2011-08 2011-05 Article http://purl.org/eprint/type/JournalArticle 0020-1669 1520-510X http://hdl.handle.net/1721.1/74058 Cao, Rui, Brian D. McCarthy, and Stephen J. Lippard. “Immobilization, Trapping, and Anion Exchange of Perrhenate Ion Using Copper-Based Tripodal Complexes.” Inorganic Chemistry 50.19 (2011): 9499–9507. https://orcid.org/0000-0002-2693-4982 en_US http://dx.doi.org/10.1021/ic201172r Inorganic Chemistry Creative Commons Attribution-Noncommercial-Share Alike 3.0 http://creativecommons.org/licenses/by-nc-sa/3.0/ application/pdf American Chemical Society (ACS) Prof. Lippard via Erja Kajosalo |
| spellingShingle | Cao, Rui McCarthy, Brian D. Lippard, Stephen J. Immobilization, Trapping, and Anion Exchange of Perrhenate Ion Using Copper-Based Tripodal Complexes |
| title | Immobilization, Trapping, and Anion Exchange of Perrhenate Ion Using Copper-Based Tripodal Complexes |
| title_full | Immobilization, Trapping, and Anion Exchange of Perrhenate Ion Using Copper-Based Tripodal Complexes |
| title_fullStr | Immobilization, Trapping, and Anion Exchange of Perrhenate Ion Using Copper-Based Tripodal Complexes |
| title_full_unstemmed | Immobilization, Trapping, and Anion Exchange of Perrhenate Ion Using Copper-Based Tripodal Complexes |
| title_short | Immobilization, Trapping, and Anion Exchange of Perrhenate Ion Using Copper-Based Tripodal Complexes |
| title_sort | immobilization trapping and anion exchange of perrhenate ion using copper based tripodal complexes |
| url | http://hdl.handle.net/1721.1/74058 https://orcid.org/0000-0002-2693-4982 |
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