Electrochemical Evidence for Hemilabile Coordination of 1,3-Dimethyllumazine to [1,1 '-Bis(diorganophosphino)ferrocene]copper(I)
The complex cations [Cu(dippf)(DML)](+) ([1](+)) and [Cu(dppf)(DML)](+) ([2](+)), where dippf = 1,1'-bis(diisopropylphosphino)ferrocene, dppf = 1,1'-bis(diphenylphosphino)ferrocene, and DML = 1,3-dimethyllumazine, were prepared and crystallized as BF4- or PF6- salts. Structure determinatio...
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ftczacademyscien:oai:asep.lib.cas.cz:CavUnEpca/0434726 2024-02-04T10:00:01+01:00 Electrochemical Evidence for Hemilabile Coordination of 1,3-Dimethyllumazine to [1,1 '-Bis(diorganophosphino)ferrocene]copper(I) Jana, R. Sarkar, B. Strobel, S. Mobin, S. M. Kaim, W. Fiedler, J. (Jan) 2014 https://doi.org/10.1021/om500039a http://hdl.handle.net/11104/0238723 eng eng doi:10.1021/om500039a urn:pissn: 0276-7333 urn:eissn: 1520-6041 http://hdl.handle.net/11104/0238723 electrochemistry metal complexes crystal structure info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion 2014 ftczacademyscien https://doi.org/10.1021/om500039a 2024-01-09T17:29:23Z The complex cations [Cu(dippf)(DML)](+) ([1](+)) and [Cu(dppf)(DML)](+) ([2](+)), where dippf = 1,1'-bis(diisopropylphosphino)ferrocene, dppf = 1,1'-bis(diphenylphosphino)ferrocene, and DML = 1,3-dimethyllumazine, were prepared and crystallized as BF4- or PF6- salts. Structure determinations of the tetrafluoroborates revealed asymmetric O-4,N-5 chelation of DML to copper(I) with longer Cu-O bonds of about 2.25 angstrom. Reversible oxidation to [1](2+) and [2](2+) proceeds at the ferrocene units, while reduction leads to the neutral radical complexes [1] and [2] with the unpaired electron localized on the DML ligand. The occurrence of two voltammetric steps for the one-electron-reduction process is attributed to a two-species equilibrium caused by the hemilabile coordination of DML. Electrochemical and spectroelectrochemical measurements (UV-vis, IR) reveal increased coordination lability of the reduced complexes and their slow fragmentation. Article in Journal/Newspaper DML The Czech Academy of Sciences: Publication Activity (ASEP) Organometallics 33 18 4784 4791 |
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The Czech Academy of Sciences: Publication Activity (ASEP) |
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ftczacademyscien |
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English |
topic |
electrochemistry metal complexes crystal structure |
spellingShingle |
electrochemistry metal complexes crystal structure Jana, R. Sarkar, B. Strobel, S. Mobin, S. M. Kaim, W. Fiedler, J. (Jan) Electrochemical Evidence for Hemilabile Coordination of 1,3-Dimethyllumazine to [1,1 '-Bis(diorganophosphino)ferrocene]copper(I) |
topic_facet |
electrochemistry metal complexes crystal structure |
description |
The complex cations [Cu(dippf)(DML)](+) ([1](+)) and [Cu(dppf)(DML)](+) ([2](+)), where dippf = 1,1'-bis(diisopropylphosphino)ferrocene, dppf = 1,1'-bis(diphenylphosphino)ferrocene, and DML = 1,3-dimethyllumazine, were prepared and crystallized as BF4- or PF6- salts. Structure determinations of the tetrafluoroborates revealed asymmetric O-4,N-5 chelation of DML to copper(I) with longer Cu-O bonds of about 2.25 angstrom. Reversible oxidation to [1](2+) and [2](2+) proceeds at the ferrocene units, while reduction leads to the neutral radical complexes [1] and [2] with the unpaired electron localized on the DML ligand. The occurrence of two voltammetric steps for the one-electron-reduction process is attributed to a two-species equilibrium caused by the hemilabile coordination of DML. Electrochemical and spectroelectrochemical measurements (UV-vis, IR) reveal increased coordination lability of the reduced complexes and their slow fragmentation. |
format |
Article in Journal/Newspaper |
author |
Jana, R. Sarkar, B. Strobel, S. Mobin, S. M. Kaim, W. Fiedler, J. (Jan) |
author_facet |
Jana, R. Sarkar, B. Strobel, S. Mobin, S. M. Kaim, W. Fiedler, J. (Jan) |
author_sort |
Jana, R. |
title |
Electrochemical Evidence for Hemilabile Coordination of 1,3-Dimethyllumazine to [1,1 '-Bis(diorganophosphino)ferrocene]copper(I) |
title_short |
Electrochemical Evidence for Hemilabile Coordination of 1,3-Dimethyllumazine to [1,1 '-Bis(diorganophosphino)ferrocene]copper(I) |
title_full |
Electrochemical Evidence for Hemilabile Coordination of 1,3-Dimethyllumazine to [1,1 '-Bis(diorganophosphino)ferrocene]copper(I) |
title_fullStr |
Electrochemical Evidence for Hemilabile Coordination of 1,3-Dimethyllumazine to [1,1 '-Bis(diorganophosphino)ferrocene]copper(I) |
title_full_unstemmed |
Electrochemical Evidence for Hemilabile Coordination of 1,3-Dimethyllumazine to [1,1 '-Bis(diorganophosphino)ferrocene]copper(I) |
title_sort |
electrochemical evidence for hemilabile coordination of 1,3-dimethyllumazine to [1,1 '-bis(diorganophosphino)ferrocene]copper(i) |
publishDate |
2014 |
url |
https://doi.org/10.1021/om500039a http://hdl.handle.net/11104/0238723 |
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DML |
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DML |
op_relation |
doi:10.1021/om500039a urn:pissn: 0276-7333 urn:eissn: 1520-6041 http://hdl.handle.net/11104/0238723 |
op_doi |
https://doi.org/10.1021/om500039a |
container_title |
Organometallics |
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33 |
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18 |
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4784 |
op_container_end_page |
4791 |
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1789965093733138432 |