DSpace
 

DSpace at IIT Bombay >
IITB Publications >
Article >

Please use this identifier to cite or link to this item: http://dspace.library.iitb.ac.in/jspui/handle/10054/12869

Title: Synthesis and spectro-electrochemical aspects of [Ru-II(trpy)(pdt)(X)](n+) (trpy=2,2 ': 6 ',2 ''-terpyridine, pdt=5,6-diphenyl-3-pyridyl-as-triazine, X = Cl-, CH3CN, NO2-, NO+, NO center dot) - Electrophilicity of {Ru-II-NO+} and photolability of {Ru-II-NO center dot}
Authors: MAJI, S
CHATTERJEE, C
MOBIN, SM
LAHIRI, GK
Keywords: ruthenium terpyridine complexes
metal nitrosyl complexes
dna-binding properties
nitric-oxide
spectroelectrochemical properties
crystal-structure
electron-transfer
ancillary ligands
diruthenium(ii) complexes
photophysical aspects
Issue Date: 2007
Publisher: WILEY-V C H VERLAG GMBH
Citation: EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, (21), 3425-3434
Abstract: Nitrosylruthenium derivatives having NO+ and NO. states have been synthesized in a stepwise manner starting from [Ru-II(trpy)(pdt)(Cl)](ClO4) {[1](ClO4)} -> [Ru-II(trpy)(pdt)(CH3CN)](ClO4)(2) {[2](ClO4)(2)} -> [Ru-II(trpy)(pdt)(NO2)](ClO4) {[3](ClO4)} -> [Ru-II(trpy)(pdt)(NO+)](ClO4)(3) {[4](ClO4)(3)} -> [Ru-II(trpy)(pdt)(NO.)](ClO4)(2) {[4](ClO4)(2)} [trpy = 2,2':6',2 ''-terpyridine, pdt = 5,6-diphenyl-3-pyridyl-as-triazine]. The molecular identity of [1](ClO4) and [2](ClO4)(2), and the subsequent stereoretentive transformation of [1](ClO4) -> [2](ClO4)(2) have been authenticated by single-crystal X-ray structures. Electrochemical and spectral features are investigated as a function of the monodentate ligands (Cl-, CH3CN, NO2-, NO+, NO.). The kinetic and thermodynamic aspects of the reaction of the moderately strong electrophilic {Ru-II-NO+} center [v(NO): 1944 cm(-1)] in [4](3+) with a nucleophile such as OH- have been studied. The nitrosyl species [Ru-II(trpy)(pdt)(NO+)](3+) ([4](3+)) can be selectively reduced to [Ru-II(trpy)(pdt)(NO.)](2+) ([4](2+)) electrochemically as well as chemically by hydrazine hydrate. On exposure to light an acetonitrile solution of [Ru-II(trpy)(pdt)(NO.)](2+) ([4](2+)) undergoes slow photocleavage of the Ru-II-NO bond over a period of 4 h, resulting in the corresponding solvated species [Ru-II(trpy)(pdt)(CH3CN)](2+) ([2](2+)). The rate of photolability of the Ru-II-NO bond in [4](2+) has been monitored spectrophotometrically. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007).
URI: http://dx.doi.org/10.1002/ejic.200700143
http://dspace.library.iitb.ac.in/xmlui/handle/10054/12869
http://hdl.handle.net/10054/12869
ISSN: 1434-1948
Appears in Collections:Article

Files in This Item:

There are no files associated with this item.

View Statistics

Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.

 

Valid XHTML 1.0! DSpace Software Copyright © 2002-2010  Duraspace - Feedback