Record Details

Synthesis, Structure and Properties of a Five-Coordinate Oxophosphorus(V) meso-Triphenylcorrole

DSpace at IIT Bombay

View Archive Info
 
 
Field Value
 
Title Synthesis, Structure and Properties of a Five-Coordinate Oxophosphorus(V) meso-Triphenylcorrole
 
Creator GHOSH, A
LEE, WZ
RAVIKANTH, M
 
Subject Fluorescence
Phosphorus
Coordination modes
Corroles
TRANSITION-METAL-COMPLEXES
CORE-MODIFIED CORROLES
MOLECULAR-STRUCTURE
PHOSPHORUS COMPLEXES
OXIDATION-STATES
COORDINATION CHEMISTRY
ELECTRONIC-STRUCTURE
CHROMIUM CORROLES
GALLIUM CORROLES
PORPHYRINS
 
Description 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 angstrom 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)(OCH3)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].
 
Publisher WILEY-V C H VERLAG GMBH
 
Date 2014-10-16T13:40:05Z
2014-10-16T13:40:05Z
2012
 
Type Article
 
Identifier EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, (26)4231-4239
http://dx.doi.org/10.1002/ejic.201200651
http://dspace.library.iitb.ac.in/jspui/handle/100/15689
 
Language en