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http://nopr.niscpr.res.in/handle/123456789/18060| Title: | Photoreduction of Co(en)2Cl(RC6H4NH2)2+ in water— isopropanol solutions: Solvent and structure reactivity correlation analysis |
| Authors: | Anbalagan, K |
| Issue Date: | Apr-2005 |
| Publisher: | NISCAIR-CSIR, India |
| IPC Code: | Int. Cl7. C07133 1/00; C07F15/06 |
| Abstract: | Photoreduction quantum yields of Co(en)2Cl(RC6H4NH2)2+ (where R = p-OMe, p-OEt, p-Me, m-Me, H and p-F) in water-isopropanol mixtures (15, 20, 25, 30, 35 and 40% (v/v) organic cosolvent) at 25°C, ionic strength i = 0.1 M (NaNO3), have been subjected to phenomenological model of solvent effect. The quantum yield values obtained from different solvent compositions are fitted into a simple and multiple regression model equations to understand and quantify medium influence. The solvent effects are explained by statistical equations, which can establish nonspecific (Laidler-Eyring, 1/εr, plot), specific (extended Krygowski-Fawcett 's, ETNand β) and both nonspecific/specific (Kamlet-Taft's, α , β, and π*) solvation effects. A quantitative measure on solvation effect using the respective coefficients is attempted. The observed substituent effect (Hammett 's σ plot) is explained for the electronic contribution leading to stability of excited state [COII .L]2+ or less polar geminate radical pair [COII .L]2+. From the results it is concluded that photoreduction proceeds th rough a less polar geminate radical pair [COII .L]2+ that is stabilized by an electron donating group (p-OMe) of the sixth ligand (RC6H4NH2) or by decreasing the polarity of the medium. |
| Page(s): | 667-672 |
| ISSN: | 0975-0975(Online); 0376-4710(Print) |
| Appears in Collections: | IJC-A Vol.44A(04) [April 2005] |
Files in This Item:
| File | Description | Size | Format | |
|---|---|---|---|---|
| IJCA 44A(4) 667-672.pdf | 1.38 MB | Adobe PDF | View/Open |
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