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Ruthenium-, osmium- and cobalt-ion mediated selective activation of a C-Cl bond. Direct and spontaneous aromatic thiolation reaction via C-S bond cleavage

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Title Ruthenium-, osmium- and cobalt-ion mediated selective activation of a C-Cl bond. Direct and spontaneous aromatic thiolation reaction via C-S bond cleavage
 
Creator SANTRA, BK
LAHIRI, GK
 
Subject alkyl-halides
h activation
complexes
chemistry
oxidation
reduction
spectra
 
Description The reactions of KSC(S)OEt and NaSC(S)NEt2 with the complexes [RuL2Cl2] 1a, [OsL2Br2] 1b and [CoL3[ClO4](2).H2O 1c [L = 2-(o-chlorophenylazo)pyridine, 2-(o-ClC6H4N=N)C5H4N] in boiling dimethylformamide solvent resulted in [(RuL)-L-II'(2)] 3a, [(OsL)-L-II'(2)] 3b and [(CoL)-L-III'(2)][ClO4] 3c respectively [L' = 2-(o-SC6H4N=N)C5H4N]. In complexes 3 the o-carbon-chlorine bond of the pendant phenyl ring of the parent ligand L has been selectively and directly thiolated via carbon-sulfur bond cleavage of the dithiocarbonate and dithiocarbamate molecules, Two such newly formed tridentate thiolated ligands (L') are bound to the metal ions in a meridional fashion. The reactions are spontaneous in the case of dithiocarbonate as thiolating agent, but relatively slow and incomplete for dithiocarbamate. During the thiolation reaction the metal ion in the cobalt complex is oxidised from the starting Co-II in 1c to Co-III in the final product 3c. The reactions are highly sensitive to the nature of the solvent used, taking place only in those having high boiling points and polarities. The meridional configuration (cis-trans-cis with respect to sulfur, azo and pyridine nitrogens respectively) of 3 has been established by H-1 and C-13 NMR spectroscopy. The complexes exhibit two MLCT transitions in the visible region and intraligand (pi-pi*, n-pi*) transitions in the UV region. In acetonitrile solution they display reversible M-III-M-II reduction potentials at 0.43 V for Ru (3a), 0.36 V for Os (3b) and -0.14 V for Co (3c) versus the saturated calomel electrode.
 
Publisher ROYAL SOC CHEMISTRY
 
Date 2011-08-28T17:36:51Z
2011-12-26T12:58:08Z
2011-12-27T05:47:36Z
2011-08-28T17:36:51Z
2011-12-26T12:58:08Z
2011-12-27T05:47:36Z
1998
 
Type Article
 
Identifier JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, (10), 1613-1618
0300-9246
http://dx.doi.org/10.1039/a708641e
http://dspace.library.iitb.ac.in/xmlui/handle/10054/11801
http://hdl.handle.net/10054/11801
 
Language en