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Structural, Spectral, Biological and Electrochemical Studies Of Some ...

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thione thiol<br />

Fig 1.1<br />

The existence of two forms of E isomer viz E l <strong>and</strong> Ell is reported. The E l<br />

isomer has more intermolecular hydrogen bonding than Ell [18]. The isomers are<br />

represented in the Figure.l.2<br />

The E <strong>and</strong> Z isomers of 2-formylpyridine thiosemicarbazones as well as those<br />

of other heterocyclic thiosemicarbazones have been separated <strong>and</strong> characterized [19].<br />

The subtle difference in stereochemistry between isomers was based upon the degree<br />

of shielding observed for the 2N proton ofthe Z isomer, (8= 14.15 ppm).<br />

However in most complexes thiosemicarbazones coordinate as bidentate<br />

lig<strong>and</strong> via the azomethine nitrogen <strong>and</strong> thione-thiol sulphur. When additional<br />

coordination functionality is present in the proximity of the donating centers, the<br />

lig<strong>and</strong>s will coordinate in a tridentate manner. This either can be accomplished by<br />

the neutral molecule or by the monobasic anion upon loss ofhydrogen.<br />

Besides the denticity variation, consideration of the charge distribution is<br />

complicated in thiosemicarbazones due to the existence of thione <strong>and</strong> thiol tautomers.<br />

Although the thione form predominates in the solid state, solutions of<br />

thiosemicarbazone molecules show a mixture of both tautomers. As a result,<br />

depending upon the preparative conditions, the metal complex can be cationic neutral<br />

or anionic. Most of the earlier investigations of metal thiosemicarbazone complexes<br />

have involved lig<strong>and</strong>s in the uncharged thione form, but a number of recent reports<br />

6

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