Extremely Electron‐Poor Bis(diarylmethylium)‐Substituted Ferrocenes and the First Peroxoferrocenophane
We have prepared and studied extremely electron‐poor, deeply colored dicationic 1,1'‐bis(diarylmethylium)‐substituted ferrocenes [(η5‐C5H4‐CAr2)2Fe]2+ with various aryl substituents as their [B{C6H3(CF3)2‐3,5}4]– salts. Due to the strong acceptor substitution, the redox potential for the ferroc...
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| Veröffentlicht in: | Zeitschrift für anorganische und allgemeine Chemie (1950) 2020-07, Vol.646 (13), p.712-725 |
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| container_title | Zeitschrift für anorganische und allgemeine Chemie (1950) |
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| creator | Casper, Larissa A. Oßwald, Steffen Anders, Patrick Rosenbaum, Lisa‐Catherine Winter, Rainer F. |
| description | We have prepared and studied extremely electron‐poor, deeply colored dicationic 1,1'‐bis(diarylmethylium)‐substituted ferrocenes [(η5‐C5H4‐CAr2)2Fe]2+ with various aryl substituents as their [B{C6H3(CF3)2‐3,5}4]– salts. Due to the strong acceptor substitution, the redox potential for the ferrocene‐based oxidation of the anisyl‐ or 2‐methylanisyl‐substituted congeners 1b2+ and 1c2+ is close to or even surpasses that of the second oxidation of parent ferrocene, i.e. the Cp2Fe+/2+ couple. The strongly Lewis‐acidic character of these complexes is manifest through strong interactions with donor solvents, which lead to a significant reduction of the intensities of the charge‐transfer bands in their electronic spectra and to solvatochromism. The reduced forms of the complexes tend to dimerize or oligomerize as revealed by EPR spectroscopy. Direduced 1b selectively reacts with molecular oxygen to form a peroxo‐bis(diarylmethyl)[4]ferrocenophane, which was also characterized by X‐ray crystallography. |
| doi_str_mv | 10.1002/zaac.201900347 |
| format | Article |
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Due to the strong acceptor substitution, the redox potential for the ferrocene‐based oxidation of the anisyl‐ or 2‐methylanisyl‐substituted congeners 1b2+ and 1c2+ is close to or even surpasses that of the second oxidation of parent ferrocene, i.e. the Cp2Fe+/2+ couple. The strongly Lewis‐acidic character of these complexes is manifest through strong interactions with donor solvents, which lead to a significant reduction of the intensities of the charge‐transfer bands in their electronic spectra and to solvatochromism. The reduced forms of the complexes tend to dimerize or oligomerize as revealed by EPR spectroscopy. Direduced 1b selectively reacts with molecular oxygen to form a peroxo‐bis(diarylmethyl)[4]ferrocenophane, which was also characterized by X‐ray crystallography.</description><identifier>ISSN: 0044-2313</identifier><identifier>EISSN: 1521-3749</identifier><identifier>DOI: 10.1002/zaac.201900347</identifier><language>eng</language><publisher>Weinheim: Wiley Subscription Services, Inc</publisher><subject>Aromatic compounds ; Charge transfer ; Congeners ; Crystallography ; Electrochemistry ; Electronic spectra ; EPR spectroscopy ; Ferrocene ; Ferrocenes ; Ferrocenophane ; Oligomerization ; Oxidation ; Oxygen ; Peroxo compound ; Solvatochromism ; Spectroelectrochemistry ; Spectrum analysis ; Substitutes ; Tritylium</subject><ispartof>Zeitschrift für anorganische und allgemeine Chemie (1950), 2020-07, Vol.646 (13), p.712-725</ispartof><rights>2020 The Authors. Published by Wiley‐VCH Verlag GmbH & Co. KGaA.</rights><rights>2020. 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Notwithstanding the ProQuest Terms and Conditions, you may use this content in accordance with the terms of the License.</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c4237-9439ac44fbf7e49008fccf783dfe6fc81548915c895620244124f9bcb12b40f53</citedby><cites>FETCH-LOGICAL-c4237-9439ac44fbf7e49008fccf783dfe6fc81548915c895620244124f9bcb12b40f53</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://onlinelibrary.wiley.com/doi/pdf/10.1002%2Fzaac.201900347$$EPDF$$P50$$Gwiley$$Hfree_for_read</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fzaac.201900347$$EHTML$$P50$$Gwiley$$Hfree_for_read</linktohtml><link.rule.ids>314,780,784,1416,27922,27923,45572,45573</link.rule.ids></links><search><creatorcontrib>Casper, Larissa A.</creatorcontrib><creatorcontrib>Oßwald, Steffen</creatorcontrib><creatorcontrib>Anders, Patrick</creatorcontrib><creatorcontrib>Rosenbaum, Lisa‐Catherine</creatorcontrib><creatorcontrib>Winter, Rainer F.</creatorcontrib><title>Extremely Electron‐Poor Bis(diarylmethylium)‐Substituted Ferrocenes and the First Peroxoferrocenophane</title><title>Zeitschrift für anorganische und allgemeine Chemie (1950)</title><description>We have prepared and studied extremely electron‐poor, deeply colored dicationic 1,1'‐bis(diarylmethylium)‐substituted ferrocenes [(η5‐C5H4‐CAr2)2Fe]2+ with various aryl substituents as their [B{C6H3(CF3)2‐3,5}4]– salts. Due to the strong acceptor substitution, the redox potential for the ferrocene‐based oxidation of the anisyl‐ or 2‐methylanisyl‐substituted congeners 1b2+ and 1c2+ is close to or even surpasses that of the second oxidation of parent ferrocene, i.e. the Cp2Fe+/2+ couple. The strongly Lewis‐acidic character of these complexes is manifest through strong interactions with donor solvents, which lead to a significant reduction of the intensities of the charge‐transfer bands in their electronic spectra and to solvatochromism. The reduced forms of the complexes tend to dimerize or oligomerize as revealed by EPR spectroscopy. Direduced 1b selectively reacts with molecular oxygen to form a peroxo‐bis(diarylmethyl)[4]ferrocenophane, which was also characterized by X‐ray crystallography.</description><subject>Aromatic compounds</subject><subject>Charge transfer</subject><subject>Congeners</subject><subject>Crystallography</subject><subject>Electrochemistry</subject><subject>Electronic spectra</subject><subject>EPR spectroscopy</subject><subject>Ferrocene</subject><subject>Ferrocenes</subject><subject>Ferrocenophane</subject><subject>Oligomerization</subject><subject>Oxidation</subject><subject>Oxygen</subject><subject>Peroxo compound</subject><subject>Solvatochromism</subject><subject>Spectroelectrochemistry</subject><subject>Spectrum analysis</subject><subject>Substitutes</subject><subject>Tritylium</subject><issn>0044-2313</issn><issn>1521-3749</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2020</creationdate><recordtype>article</recordtype><sourceid>24P</sourceid><sourceid>WIN</sourceid><recordid>eNqFkL1Ow0AQhE8IJEKgpbZEA4XD3o9jXxmiBJAiEQloaCz7vKc4sn3h7ixiKh6BZ-RJcBQEJdUWM9-OZgg5pzCiAOz6PcvUiAGVAFzEB2RAI0ZDHgt5SAYAQoSMU35MTpxbAwCFKBqQ9WzrLdZYdcGsQuWtab4-PpfG2OCmdJdFmdmuqtGvuqps66tee2xz50vfeiyCOVprFDbogqwpAr_CYF5a54MlWrM1-kc2m1XW4Ck50lnl8OznDsnzfPY0vQsXD7f308kiVILxOJSCy0wJoXMdo-jLJFopHSe80DjWKqGRSCSNVCKjMQMmBGVCy1zllOUCdMSH5GL_d2PNa4vOp2vT2qaPTNkugSUJyN412ruUNc5Z1OnGlnXfNqWQ7vZMd3umv3v2gNwDb2WF3T_u9GUymf6x3z1kfUM</recordid><startdate>20200715</startdate><enddate>20200715</enddate><creator>Casper, Larissa A.</creator><creator>Oßwald, Steffen</creator><creator>Anders, Patrick</creator><creator>Rosenbaum, Lisa‐Catherine</creator><creator>Winter, Rainer F.</creator><general>Wiley Subscription Services, Inc</general><scope>24P</scope><scope>WIN</scope><scope>AAYXX</scope><scope>CITATION</scope></search><sort><creationdate>20200715</creationdate><title>Extremely Electron‐Poor Bis(diarylmethylium)‐Substituted Ferrocenes and the First Peroxoferrocenophane</title><author>Casper, Larissa A. ; Oßwald, Steffen ; Anders, Patrick ; Rosenbaum, Lisa‐Catherine ; Winter, Rainer F.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c4237-9439ac44fbf7e49008fccf783dfe6fc81548915c895620244124f9bcb12b40f53</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2020</creationdate><topic>Aromatic compounds</topic><topic>Charge transfer</topic><topic>Congeners</topic><topic>Crystallography</topic><topic>Electrochemistry</topic><topic>Electronic spectra</topic><topic>EPR spectroscopy</topic><topic>Ferrocene</topic><topic>Ferrocenes</topic><topic>Ferrocenophane</topic><topic>Oligomerization</topic><topic>Oxidation</topic><topic>Oxygen</topic><topic>Peroxo compound</topic><topic>Solvatochromism</topic><topic>Spectroelectrochemistry</topic><topic>Spectrum analysis</topic><topic>Substitutes</topic><topic>Tritylium</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Casper, Larissa A.</creatorcontrib><creatorcontrib>Oßwald, Steffen</creatorcontrib><creatorcontrib>Anders, Patrick</creatorcontrib><creatorcontrib>Rosenbaum, Lisa‐Catherine</creatorcontrib><creatorcontrib>Winter, Rainer F.</creatorcontrib><collection>Wiley-Blackwell Open Access Titles</collection><collection>Wiley Free Content</collection><collection>CrossRef</collection><jtitle>Zeitschrift für anorganische und allgemeine Chemie (1950)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Casper, Larissa A.</au><au>Oßwald, Steffen</au><au>Anders, Patrick</au><au>Rosenbaum, Lisa‐Catherine</au><au>Winter, Rainer F.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Extremely Electron‐Poor Bis(diarylmethylium)‐Substituted Ferrocenes and the First Peroxoferrocenophane</atitle><jtitle>Zeitschrift für anorganische und allgemeine Chemie (1950)</jtitle><date>2020-07-15</date><risdate>2020</risdate><volume>646</volume><issue>13</issue><spage>712</spage><epage>725</epage><pages>712-725</pages><issn>0044-2313</issn><eissn>1521-3749</eissn><abstract>We have prepared and studied extremely electron‐poor, deeply colored dicationic 1,1'‐bis(diarylmethylium)‐substituted ferrocenes [(η5‐C5H4‐CAr2)2Fe]2+ with various aryl substituents as their [B{C6H3(CF3)2‐3,5}4]– salts. Due to the strong acceptor substitution, the redox potential for the ferrocene‐based oxidation of the anisyl‐ or 2‐methylanisyl‐substituted congeners 1b2+ and 1c2+ is close to or even surpasses that of the second oxidation of parent ferrocene, i.e. the Cp2Fe+/2+ couple. The strongly Lewis‐acidic character of these complexes is manifest through strong interactions with donor solvents, which lead to a significant reduction of the intensities of the charge‐transfer bands in their electronic spectra and to solvatochromism. The reduced forms of the complexes tend to dimerize or oligomerize as revealed by EPR spectroscopy. Direduced 1b selectively reacts with molecular oxygen to form a peroxo‐bis(diarylmethyl)[4]ferrocenophane, which was also characterized by X‐ray crystallography.</abstract><cop>Weinheim</cop><pub>Wiley Subscription Services, Inc</pub><doi>10.1002/zaac.201900347</doi><tpages>14</tpages><oa>free_for_read</oa></addata></record> |
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| source | Wiley Online Library Journals Frontfile Complete |
| subjects | Aromatic compounds Charge transfer Congeners Crystallography Electrochemistry Electronic spectra EPR spectroscopy Ferrocene Ferrocenes Ferrocenophane Oligomerization Oxidation Oxygen Peroxo compound Solvatochromism Spectroelectrochemistry Spectrum analysis Substitutes Tritylium |
| title | Extremely Electron‐Poor Bis(diarylmethylium)‐Substituted Ferrocenes and the First Peroxoferrocenophane |
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