Abstract
Treatment of six-coordinate (5,10,15-triphenylcorrole) dihydroxyphosphorus(V) [P(TPC)(OH)2] with trifluoroacetic acid (TFA) in CH2Cl2 for 30 min at room temperature followed by recrystallization gave stable five-coordinate (5,10,15-triphenylcorrole) oxophosphorus(V) [P(TPC)O] in quantitative yield. The formation of [P(TPC)O] from [P(TPC)(OH)2] in the presence of TFA was also monitored by NMR, absorption and fluorescence spectroscopic titration studies. The structure of the isolated [P(TPC)O] was confirmed by X-ray crystallography. In [P(TPC)O], the corrole ring is distorted, and the PV ion is displaced by 0.456 Å from the N4 plane towards the axial oxygen atom. This is unlike six-coordinate (5,10,15-triphenylcorrole)dimethoxyphosphorus(V) [P(TPC)(OCH3)2], in which the PV ion lies in the porphyrin plane. NMR, absorption and fluorescence spectroscopy and electrochemical studies indicate that [P(TPC)O] exhibits interesting and distinct properties, which differ from the six-coordinate [P(TPC)(OCH 3)2]. Attempts to reduce the PV complex [P(TPC)O] to its corresponding PIII complex by treating it with LiAlH4 resulted in the formation of six-coordinate (5,10,15-triphenylcorrole)dihydridophosphorus(V) [P(TPC)H2].
Original language | English |
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Pages (from-to) | 4231-4239 |
Number of pages | 9 |
Journal | European Journal of Inorganic Chemistry |
Issue number | 26 |
DOIs | |
Publication status | Published - 2012 Sept |
Keywords
- Coordination modes
- Corroles
- Fluorescence
- Phosphorus
ASJC Scopus subject areas
- Inorganic Chemistry
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CCDC 870321: Experimental Crystal Structure Determination
Ghosh, A. (Creator), Lee, W. (Creator) & Ravikanth, M. (Creator), Unknown Publisher, 2013
DOI: 10.5517/ccy6mwm, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccy6mwm&sid=DataCite
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