摘要
Treatment of six-coordinate (5,10,15-triphenylcorrole) dihydroxyphosphorus(V) [P(TPC)(OH) 2] with trifluoroacetic acid (TFA) in CH 2Cl 2 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 P V ion is displaced by 0.456 Å from the N 4 plane towards the axial oxygen atom. This is unlike six-coordinate (5,10,15-triphenylcorrole)dimethoxyphosphorus(V) [P(TPC)(OCH 3) 2], in which the P V 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 P V complex [P(TPC)O] to its corresponding P III complex by treating it with LiAlH 4 resulted in the formation of six-coordinate (5,10,15-triphenylcorrole)dihydridophosphorus(V) [P(TPC)H 2].
| 原文 | 英語 |
|---|---|
| 頁（從 - 到） | 4231-4239 |
| 頁數 | 9 |
| 期刊 | European Journal of Inorganic Chemistry |
| 發行號 | 26 |
| DOIs | |
| 出版狀態 | 已發佈 - 2012 九月 1 |
指紋
ASJC Scopus subject areas
- Inorganic Chemistry
引用此文
Synthesis, structure and properties of a five-coordinate oxophosphorus(V) meso-triphenylcorrole. / Ghosh, Avijit; Lee, Way-Zen; Ravikanth, Mangalampalli.
於: European Journal of Inorganic Chemistry, 編號 26, 01.09.2012, p. 4231-4239.研究成果: 雜誌貢獻 › 文章
}
TY - JOUR
T1 - Synthesis, structure and properties of a five-coordinate oxophosphorus(V) meso-triphenylcorrole
AU - Ghosh, Avijit
AU - Lee, Way-Zen
AU - Ravikanth, Mangalampalli
PY - 2012/9/1
Y1 - 2012/9/1
N2 - Treatment of six-coordinate (5,10,15-triphenylcorrole) dihydroxyphosphorus(V) [P(TPC)(OH) 2] with trifluoroacetic acid (TFA) in CH 2Cl 2 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 P V ion is displaced by 0.456 Å from the N 4 plane towards the axial oxygen atom. This is unlike six-coordinate (5,10,15-triphenylcorrole)dimethoxyphosphorus(V) [P(TPC)(OCH 3) 2], in which the P V 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 P V complex [P(TPC)O] to its corresponding P III complex by treating it with LiAlH 4 resulted in the formation of six-coordinate (5,10,15-triphenylcorrole)dihydridophosphorus(V) [P(TPC)H 2].
AB - Treatment of six-coordinate (5,10,15-triphenylcorrole) dihydroxyphosphorus(V) [P(TPC)(OH) 2] with trifluoroacetic acid (TFA) in CH 2Cl 2 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 P V ion is displaced by 0.456 Å from the N 4 plane towards the axial oxygen atom. This is unlike six-coordinate (5,10,15-triphenylcorrole)dimethoxyphosphorus(V) [P(TPC)(OCH 3) 2], in which the P V 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 P V complex [P(TPC)O] to its corresponding P III complex by treating it with LiAlH 4 resulted in the formation of six-coordinate (5,10,15-triphenylcorrole)dihydridophosphorus(V) [P(TPC)H 2].
KW - Coordination modes
KW - Corroles
KW - Fluorescence
KW - Phosphorus
UR - http://www.scopus.com/inward/record.url?scp=84865857876&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84865857876&partnerID=8YFLogxK
U2 - 10.1002/ejic.201200651
DO - 10.1002/ejic.201200651
M3 - Article
AN - SCOPUS:84865857876
SP - 4231
EP - 4239
JO - Chemische Berichte
JF - Chemische Berichte
SN - 0009-2940
IS - 26
ER -