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A facile and preferential synthesis of the complexes, cis-trans-cis-Ru-II[NC5H4-N = N-C6H4(R)](2) (R = H, o-Me/Cl, m-Me/Cl-,Cl- p-Me/Cl). Synthesis, spectroscopic characterization and electron-transfer properties

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Title A facile and preferential synthesis of the complexes, cis-trans-cis-Ru-II[NC5H4-N = N-C6H4(R)](2) (R = H, o-Me/Cl, m-Me/Cl-,Cl- p-Me/Cl). Synthesis, spectroscopic characterization and electron-transfer properties
 
Creator MUNSHI, P
SAMANTA, R
LAHIRI, GK
 
Subject redox properties
ruthenium complex
crystal-structure
oxidation levels
metal oxidation
charge-transfer
chemistry
family
ligands
spectra
ruthenium
synthesis
spectra
redox
 
Description A group of seven complexes of the type ctc-(RuL2Cl2)-L-II (2a-2g) (L = NC5H4-N=N-C6H5(R), R = H, o-Me/Cl, m-Me/Cl, p-Me/Cl and ctc = cic-trans-cis with respect to chlorides, pyridine and azo nitrogens, respectively) have been synthesized and characterized. The complexes are diamagnetic (Ru-II, t(2g)(6), S = 0) and electrically neutral. The molecular geometry of the complexes (2) in solution has been established by H-1 NMR spectroscopy. They exhibit a strong metal to ligand charge-transfer band in the range 582-603 nm and intra ligand pi-pi* transition near 320 nm. In acetonitrile solution the complexes display reversible ruthenium(II) reversible arrow ruthenium(III) oxidation couples in the range 1.02 --> 1.36 V vs SCE. Two successive quasi-reversible ligand reductions are observed for each complex in the ranges -0.42 --> -0.60 V and -0.68 --> -0.85 V vs SCE, respectively. The complexes 2a and 2e have been oxidized tb the corresponding trivalent species (3a and 3e) by using HNO3 as oxidizing agent and isolated in solid state as perchlorate salts. Complexes are one-electron paramagnets (Ru-III, t(2g)(5), S = 1/2) and show 1:1 conductivity in acetonitrile solution. The presence of perchlorate counter ion in the complexes has been evidenced by the strong infrared bands near 1100 and 600 cm(-1). Complexes exhibit a strong ligand to metal charge-transfer band near 530 nm and intra ligand pi-pi* transition near 370 nm. In glassy condition (77 K) complexes display rhombic EPR spectra corresponding to the distorted octahedral geometry. (C) 1998 . .
 
Publisher PERGAMON-ELSEVIER SCIENCE LTD
 
Date 2011-08-23T05:57:11Z
2011-12-26T12:56:18Z
2011-12-27T05:44:48Z
2011-08-23T05:57:11Z
2011-12-26T12:56:18Z
2011-12-27T05:44:48Z
1998
 
Type Article
 
Identifier POLYHEDRON, 17(11-12), 1913-1922
0277-5387
http://dx.doi.org/10.1016/S0277-5387(97)00512-3
http://dspace.library.iitb.ac.in/xmlui/handle/10054/10412
http://hdl.handle.net/10054/10412
 
Language en