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
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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 -