Palladium Vacataporphyrin Reveals Conformational Rearrangements Involving Hückel and Möbius Macrocyclic Topologies.
5,10,15,20-Tetraaryl-21-vacataporphyrin (butadieneporphyrin, an annulene-porphyrin hybrid) which contains a vacant space instead of heteroatomic bridge acts as a ligand toward palladium(II). The metal ion of square-planar coordination geometry is firmly held via three pyrrolic nitrogen atoms where t...
| Published in: | Journal of the American Chemical Society Vol. 130; no. 19; pp. 6182 - 6196 |
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| Main Authors: | , , , , , |
| Format: | Article |
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American Chemical Society
5/14/2008
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| Subjects: | |
| Online Access: | View this record in EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=32064392&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 32064392 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 5/14/2008 vid: 130 iid: 19 pid: 997 pub: American Chemical Society artinfo: ui: 32064392 10.1021/ja711039c ppf: 6182 ppct: 14 formats: tig: atl: Palladium Vacataporphyrin Reveals Conformational Rearrangements Involving Hückel and Möbius Macrocyclic Topologies. aug: au: Pacholska-Dudziak, Ewa Skonieczny, Janusz Pawlicki, Miłosz Szterenberg, Ludmiła Ciunik, Zbigniew Latos-Grażyński, Lechosław affil: Department of Chemistry, University of Wrocław, Joliot-Curie 14, 50 383 Wrocław, Poland su: Physical & theoretical chemistry research Palladium Conformational analysis Macrocyclic compounds Nuclear magnetic resonance Density functionals sug: subj: Physical & theoretical chemistry research Palladium Conformational analysis Macrocyclic compounds Nuclear magnetic resonance Density functionals ab: 5,10,15,20-Tetraaryl-21-vacataporphyrin (butadieneporphyrin, an annulene-porphyrin hybrid) which contains a vacant space instead of heteroatomic bridge acts as a ligand toward palladium(II). The metal ion of square-planar coordination geometry is firmly held via three pyrrolic nitrogen atoms where the fourth coordination place is occupied by a monodentate ligand or by an annulene part of vacataporphyrin. The macrocycle reveals the unique structural flexibility triggered by coordination of palladium. The structural rearrangements engage the C(20)C(1)C(2)C(3)C(4)C(5) annulene fragment which serves as a linker between two pyrrolic rings of vacataporphyrin albeit the significant ruffling of the tripyrrolic block is also of importance. Two fundamental modes of interactions between the palladium ion and annulene moiety have been recognized. The first one resembles an η-type interaction and involves the C(2)C(3) unit of the butadiene part. Alternatively the profound conformational adjustments allowed an in-plane coordination through the deprotonated trigonally hybridized C(2) center of butadiene. The coordinated vacataporphyrin acquires Hückel or extremely rare Möbius topologies readily reflected by spectroscopic properties. The palladium vacataporphyrin complexes reveal Hückel aromaticity or Möbius antiaromaticity of [18]annulene applying the butadiene fragment of vacataporphyrin as a topology selector. The properties of specific conformers were determined using H NMR and density functional theory calculations. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2008 holdings: @attributes: islocal: N |
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