meso-Porphyrinylphosphine Oxides: Mono- and Bidentate Ligands for Supramolecular Chemistry and the Crystal Structures of Monomeric {[10,20-Diphenylporphyrinatonickel(II)-5,15-diyl]-bis-[P(O)Ph2] and Polymeric Self-Coordinated {[10,20-Diphenylporphyrinatozinc(II)-5,15-diyl]-bis-[P(O)Ph2]}
| Autor: | John C. McMurtrie, Dennis P. Arnold, Martin P. Duriska, Peter Turner, Farzad Atefi |
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| Rok vydání: | 2006 |
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| Zdroj: | Inorganic Chemistry. 45:6479-6489 |
| ISSN: | 1520-510X 0020-1669 |
| DOI: | 10.1021/ic060372u |
| Popis: | A series of porphyrins substituted in one or two meso positions by diphenylphosphine oxide groups has been prepared by the palladium-catalyzed reaction of diphenylphosphine or its oxide with the corresponding bromoporphyrins. Compounds {MDPP−[P(O)Ph2]n} (M = H2, Ni, Zn; H2DPP = 5,15-diphenylporphyrin; n = 1, 2) were isolated in yields of 60−95%. The reaction is believed to proceed via the conventional oxidative addition, phosphination, and reductive elimination steps, as the stoichiometric reaction of η1-palladio(II) porphyrin [PdBr(H2DPP)(dppe)] (H2DPP = 5,15-diphenylporphyrin; dppe = 1,2-bis(diphenylphosphino)ethane) with diphenylphosphine oxide also results in the desired mono-porphyrinylphosphine oxide [H2DPP−P(O)Ph2]. Attempts to isolate the tertiary phosphines failed due to their extreme air-sensitivity. Variable-temperature 1H NMR studies of [H2DPP−P(O)Ph2] revealed an intrinsic lack of symmetry, while fluorescence spectroscopy showed that the phosphine oxide group does not behave as a “heavy atom”... |
| Databáze: | OpenAIRE |
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