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Selective Synthesis and Redox Sequence of a Heterobimetallic Nickel/Copper Complex of the Noninnocent Siamese-Twin Porphyrin
The Siamese-twin porphyrin (1H 4 ) is a redox noninnocent pyrazole-expanded porphyrin with two equivalent dibasic {N4} binding sites. It is now shown that its selective monometalation can be achieved to give the nickel(II) complex 1H 2 Ni with the second {N4} site devoid of a metal ion. This interme...
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Published in: | Inorganic chemistry 2014-08, Vol.53 (15), p.7876-7885 |
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description | The Siamese-twin porphyrin (1H 4 ) is a redox noninnocent pyrazole-expanded porphyrin with two equivalent dibasic {N4} binding sites. It is now shown that its selective monometalation can be achieved to give the nickel(II) complex 1H 2 Ni with the second {N4} site devoid of a metal ion. This intermediate is then cleanly converted to 1Ni 2 and to the first heterobimetallic Siamese-twin porphyrin 1CuNi. Structural characterization of 1H 2 Ni shows that it has the same helical structure previously seen for 1Cu 2 , 1Ni 2 , and free base 1H 6 2+ . Titration experiments suggest that the metal-devoid pocket of 1H 2 Ni can accommodate two additional protons, giving [1H 4 Ni] 2+ . Both bimetallic complexes 1Ni 2 and 1CuNi feature rich redox chemistry, similar to the recently reported 1Cu 2 , including two chemically reversible oxidations at moderate potentials between −0.3 and +0.5 V (vs Cp2Fe/Cp2Fe+). The locus of these oxidations, in singly oxidized [1Ni 2 ]+ and [1CuNi]+ as well as twice oxidized [1CuNi]2+, has been experimentally derived from comparison of the electrochemical properties of the complete series of complexes 1Cu 2 , 1Ni 2 , and 1CuNi, and from electron paramagnetic resonance (EPR) spectroscopy and X-ray absorption spectroscopy (XAS) (Ni and Cu K edges). All redox events are largely ligand-based, and in heterobimetallic 1CuNi, the first oxidation takes place within its Cu-subunit, while the second oxidation then occurs in its Ni-subunit. Adding pyridine to solutions of [1Ni 2 ]+ and [1CuNi]2+ cleanly converts them to metal-oxidized redox isomers with axial EPR spectra typical for NiIII having significant d z 2 1 character, reflecting close similarity with nickel complexes of common porphyrins. The possibility of selectively synthesizing heterobimetallic complexes 1MNi from a symmetric binucleating ligand scaffold, with the unusual situation of three distinct contiguous redox sites (M, Ni, and the porphyrin-like ligand), further expands the Siamese-twin porphyrin’s potential to serve as an adjustable platform for multielectron redox processes in chemical catalysis and in electronic applications. |
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It is now shown that its selective monometalation can be achieved to give the nickel(II) complex 1H 2 Ni with the second {N4} site devoid of a metal ion. This intermediate is then cleanly converted to 1Ni 2 and to the first heterobimetallic Siamese-twin porphyrin 1CuNi. Structural characterization of 1H 2 Ni shows that it has the same helical structure previously seen for 1Cu 2 , 1Ni 2 , and free base 1H 6 2+ . Titration experiments suggest that the metal-devoid pocket of 1H 2 Ni can accommodate two additional protons, giving [1H 4 Ni] 2+ . Both bimetallic complexes 1Ni 2 and 1CuNi feature rich redox chemistry, similar to the recently reported 1Cu 2 , including two chemically reversible oxidations at moderate potentials between −0.3 and +0.5 V (vs Cp2Fe/Cp2Fe+). The locus of these oxidations, in singly oxidized [1Ni 2 ]+ and [1CuNi]+ as well as twice oxidized [1CuNi]2+, has been experimentally derived from comparison of the electrochemical properties of the complete series of complexes 1Cu 2 , 1Ni 2 , and 1CuNi, and from electron paramagnetic resonance (EPR) spectroscopy and X-ray absorption spectroscopy (XAS) (Ni and Cu K edges). All redox events are largely ligand-based, and in heterobimetallic 1CuNi, the first oxidation takes place within its Cu-subunit, while the second oxidation then occurs in its Ni-subunit. Adding pyridine to solutions of [1Ni 2 ]+ and [1CuNi]2+ cleanly converts them to metal-oxidized redox isomers with axial EPR spectra typical for NiIII having significant d z 2 1 character, reflecting close similarity with nickel complexes of common porphyrins. The possibility of selectively synthesizing heterobimetallic complexes 1MNi from a symmetric binucleating ligand scaffold, with the unusual situation of three distinct contiguous redox sites (M, Ni, and the porphyrin-like ligand), further expands the Siamese-twin porphyrin’s potential to serve as an adjustable platform for multielectron redox processes in chemical catalysis and in electronic applications.</description><identifier>ISSN: 0020-1669</identifier><identifier>EISSN: 1520-510X</identifier><identifier>DOI: 10.1021/ic500460n</identifier><identifier>PMID: 25014112</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><subject>Copper - chemistry ; Crystallography, X-Ray ; Electron Spin Resonance Spectroscopy ; Magnetic Resonance Spectroscopy ; Nickel - chemistry ; Organometallic Compounds - chemical synthesis ; Oxidation-Reduction ; Porphyrins - chemistry</subject><ispartof>Inorganic chemistry, 2014-08, Vol.53 (15), p.7876-7885</ispartof><rights>Copyright © 2014 American Chemical Society</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a381t-59e2f71842a6ef82ebc41ccb50fe2b4bc1d677ea3d784cd7ad38fcf3624b72023</citedby><cites>FETCH-LOGICAL-a381t-59e2f71842a6ef82ebc41ccb50fe2b4bc1d677ea3d784cd7ad38fcf3624b72023</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,777,781,27905,27906</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/25014112$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Blusch, Lina K</creatorcontrib><creatorcontrib>Mitevski, Oliver</creatorcontrib><creatorcontrib>Martin-Diaconescu, Vlad</creatorcontrib><creatorcontrib>Pröpper, Kevin</creatorcontrib><creatorcontrib>DeBeer, Serena</creatorcontrib><creatorcontrib>Dechert, Sebastian</creatorcontrib><creatorcontrib>Meyer, Franc</creatorcontrib><title>Selective Synthesis and Redox Sequence of a Heterobimetallic Nickel/Copper Complex of the Noninnocent Siamese-Twin Porphyrin</title><title>Inorganic chemistry</title><addtitle>Inorg. Chem</addtitle><description>The Siamese-twin porphyrin (1H 4 ) is a redox noninnocent pyrazole-expanded porphyrin with two equivalent dibasic {N4} binding sites. It is now shown that its selective monometalation can be achieved to give the nickel(II) complex 1H 2 Ni with the second {N4} site devoid of a metal ion. This intermediate is then cleanly converted to 1Ni 2 and to the first heterobimetallic Siamese-twin porphyrin 1CuNi. Structural characterization of 1H 2 Ni shows that it has the same helical structure previously seen for 1Cu 2 , 1Ni 2 , and free base 1H 6 2+ . Titration experiments suggest that the metal-devoid pocket of 1H 2 Ni can accommodate two additional protons, giving [1H 4 Ni] 2+ . Both bimetallic complexes 1Ni 2 and 1CuNi feature rich redox chemistry, similar to the recently reported 1Cu 2 , including two chemically reversible oxidations at moderate potentials between −0.3 and +0.5 V (vs Cp2Fe/Cp2Fe+). The locus of these oxidations, in singly oxidized [1Ni 2 ]+ and [1CuNi]+ as well as twice oxidized [1CuNi]2+, has been experimentally derived from comparison of the electrochemical properties of the complete series of complexes 1Cu 2 , 1Ni 2 , and 1CuNi, and from electron paramagnetic resonance (EPR) spectroscopy and X-ray absorption spectroscopy (XAS) (Ni and Cu K edges). All redox events are largely ligand-based, and in heterobimetallic 1CuNi, the first oxidation takes place within its Cu-subunit, while the second oxidation then occurs in its Ni-subunit. Adding pyridine to solutions of [1Ni 2 ]+ and [1CuNi]2+ cleanly converts them to metal-oxidized redox isomers with axial EPR spectra typical for NiIII having significant d z 2 1 character, reflecting close similarity with nickel complexes of common porphyrins. The possibility of selectively synthesizing heterobimetallic complexes 1MNi from a symmetric binucleating ligand scaffold, with the unusual situation of three distinct contiguous redox sites (M, Ni, and the porphyrin-like ligand), further expands the Siamese-twin porphyrin’s potential to serve as an adjustable platform for multielectron redox processes in chemical catalysis and in electronic applications.</description><subject>Copper - chemistry</subject><subject>Crystallography, X-Ray</subject><subject>Electron Spin Resonance Spectroscopy</subject><subject>Magnetic Resonance Spectroscopy</subject><subject>Nickel - chemistry</subject><subject>Organometallic Compounds - chemical synthesis</subject><subject>Oxidation-Reduction</subject><subject>Porphyrins - chemistry</subject><issn>0020-1669</issn><issn>1520-510X</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2014</creationdate><recordtype>article</recordtype><recordid>eNptkEtLxDAURoMoOj4W_gHJRtBFnZu0aTtLKb5AVOwI7kqa3mK0TWrS6gz44-0w6srVvYvDge8QcsjgjAFnU60EQBSD2SATJjgEgsHzJpkAjD-L49kO2fX-FQBmYRRvkx0ugEWM8Qn5yrFB1esPpPnS9C_otafSVPQRK7ugOb4PaBRSW1NJr7FHZ0vdYi-bRit6p9UbNtPMdh06mtm2a3CxYkcRvbNGG2MVmp7mWrboMZh_akMfrOtelk6bfbJVy8bjwc_dI0-XF_PsOri9v7rJzm8DGaasD8QMeZ2wNOIyxjrlWKqIKVUKqJGXUalYFScJyrBK0khViazCtFZ1GPOoTDjwcI-crL2ds-Me3xet9gqbRhq0gy-YECzkKYhwRE_XqHLWe4d10TndSrcsGBSr2MVf7JE9-tEOZYvVH_lbdwSO14BUvni1gzPjyn9E37u9h7s</recordid><startdate>20140804</startdate><enddate>20140804</enddate><creator>Blusch, Lina K</creator><creator>Mitevski, Oliver</creator><creator>Martin-Diaconescu, Vlad</creator><creator>Pröpper, Kevin</creator><creator>DeBeer, Serena</creator><creator>Dechert, Sebastian</creator><creator>Meyer, Franc</creator><general>American Chemical Society</general><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope></search><sort><creationdate>20140804</creationdate><title>Selective Synthesis and Redox Sequence of a Heterobimetallic Nickel/Copper Complex of the Noninnocent Siamese-Twin Porphyrin</title><author>Blusch, Lina K ; Mitevski, Oliver ; Martin-Diaconescu, Vlad ; Pröpper, Kevin ; DeBeer, Serena ; Dechert, Sebastian ; Meyer, Franc</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a381t-59e2f71842a6ef82ebc41ccb50fe2b4bc1d677ea3d784cd7ad38fcf3624b72023</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2014</creationdate><topic>Copper - chemistry</topic><topic>Crystallography, X-Ray</topic><topic>Electron Spin Resonance Spectroscopy</topic><topic>Magnetic Resonance Spectroscopy</topic><topic>Nickel - chemistry</topic><topic>Organometallic Compounds - chemical synthesis</topic><topic>Oxidation-Reduction</topic><topic>Porphyrins - chemistry</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Blusch, Lina K</creatorcontrib><creatorcontrib>Mitevski, Oliver</creatorcontrib><creatorcontrib>Martin-Diaconescu, Vlad</creatorcontrib><creatorcontrib>Pröpper, Kevin</creatorcontrib><creatorcontrib>DeBeer, Serena</creatorcontrib><creatorcontrib>Dechert, Sebastian</creatorcontrib><creatorcontrib>Meyer, Franc</creatorcontrib><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>Inorganic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Blusch, Lina K</au><au>Mitevski, Oliver</au><au>Martin-Diaconescu, Vlad</au><au>Pröpper, Kevin</au><au>DeBeer, Serena</au><au>Dechert, Sebastian</au><au>Meyer, Franc</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Selective Synthesis and Redox Sequence of a Heterobimetallic Nickel/Copper Complex of the Noninnocent Siamese-Twin Porphyrin</atitle><jtitle>Inorganic chemistry</jtitle><addtitle>Inorg. Chem</addtitle><date>2014-08-04</date><risdate>2014</risdate><volume>53</volume><issue>15</issue><spage>7876</spage><epage>7885</epage><pages>7876-7885</pages><issn>0020-1669</issn><eissn>1520-510X</eissn><abstract>The Siamese-twin porphyrin (1H 4 ) is a redox noninnocent pyrazole-expanded porphyrin with two equivalent dibasic {N4} binding sites. It is now shown that its selective monometalation can be achieved to give the nickel(II) complex 1H 2 Ni with the second {N4} site devoid of a metal ion. This intermediate is then cleanly converted to 1Ni 2 and to the first heterobimetallic Siamese-twin porphyrin 1CuNi. Structural characterization of 1H 2 Ni shows that it has the same helical structure previously seen for 1Cu 2 , 1Ni 2 , and free base 1H 6 2+ . Titration experiments suggest that the metal-devoid pocket of 1H 2 Ni can accommodate two additional protons, giving [1H 4 Ni] 2+ . Both bimetallic complexes 1Ni 2 and 1CuNi feature rich redox chemistry, similar to the recently reported 1Cu 2 , including two chemically reversible oxidations at moderate potentials between −0.3 and +0.5 V (vs Cp2Fe/Cp2Fe+). The locus of these oxidations, in singly oxidized [1Ni 2 ]+ and [1CuNi]+ as well as twice oxidized [1CuNi]2+, has been experimentally derived from comparison of the electrochemical properties of the complete series of complexes 1Cu 2 , 1Ni 2 , and 1CuNi, and from electron paramagnetic resonance (EPR) spectroscopy and X-ray absorption spectroscopy (XAS) (Ni and Cu K edges). All redox events are largely ligand-based, and in heterobimetallic 1CuNi, the first oxidation takes place within its Cu-subunit, while the second oxidation then occurs in its Ni-subunit. Adding pyridine to solutions of [1Ni 2 ]+ and [1CuNi]2+ cleanly converts them to metal-oxidized redox isomers with axial EPR spectra typical for NiIII having significant d z 2 1 character, reflecting close similarity with nickel complexes of common porphyrins. The possibility of selectively synthesizing heterobimetallic complexes 1MNi from a symmetric binucleating ligand scaffold, with the unusual situation of three distinct contiguous redox sites (M, Ni, and the porphyrin-like ligand), further expands the Siamese-twin porphyrin’s potential to serve as an adjustable platform for multielectron redox processes in chemical catalysis and in electronic applications.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>25014112</pmid><doi>10.1021/ic500460n</doi><tpages>10</tpages></addata></record> |
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subjects | Copper - chemistry Crystallography, X-Ray Electron Spin Resonance Spectroscopy Magnetic Resonance Spectroscopy Nickel - chemistry Organometallic Compounds - chemical synthesis Oxidation-Reduction Porphyrins - chemistry |
title | Selective Synthesis and Redox Sequence of a Heterobimetallic Nickel/Copper Complex of the Noninnocent Siamese-Twin Porphyrin |
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