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The reaction of 2,4,6-tris(2-pyridyl)-1,3,5-triazine (tptz) with RhCl 3 ‚3H 2 O has been studied under different experimental conditions. This reaction in ethanol resulted in the formation of [Rh(tptz)Cl 3 ]‚2H 2 O (1), whereas the bis-chelate complex [Rh(tptz) 2 ][ClO 4 ] 3 ‚2H 2 O (2) was obtained in a two-step reaction in acetone; the chlorides from RhCl 3 were removed in the first step using AgClO 4 , and the ligand tptz was added in the second step. Complexes 1 and 2, when refluxed in ethanol-water (1:1), resulted in metal-promoted hydrolysis of tptz to bis-(2-pyridylcarbonyl)amide anion (bpca) and 2-picolinamide (pa), yielding the complexes [Rh(bpca)(pa)Cl][PF 6 ]‚ H 2 O (3) and [Rh(bpca) 2 ][ClO 4 ] (6), respectively. A mixed-ligand complex, [Rh(bpca)(tpy)][PF 6 ] 2 ‚CH 3 CN (4), was obtained by the reaction of either 1 with tpy or [Rh(tpy)Cl 3 ] (5) with tptz in ethanol-water medium. The crystal structures of complexes 1 and 4 have been determined. Crystal data: complex 1, monoclinic, P2 1 /c, a ) 11.642(2) Å, b ) 7.302(2) Å, c ) 24.332(3) Å, β ) 96.420(10)°, Z ) 4, R ) 0.040, and wR2 ) 0.117; complex 4, triclinic, P1 h, a ) 9.581(1) Å, b ) 12.933(2) Å, c ) 14.493(2) Å, R ) 82.480(10)°, β ) 71.810(10)°, γ ) 75.100(10)°, Z ) 2, R ) 0.030, and wR2 ) 0.082. The two water molecules of complex 1 make short contacts with the carbon atoms adjacent to the metal-bound nitrogen atom of the triazine ring; this observation provides some insight about the "intermediate" of the hydrolysis. X-ray and NMR data suggest that the electron-withdrawing effect of the metal ion is the major responsible factor for the hydrolysis of tptz. The cyclic voltammograms of the complexes exhibit a metal-based 2e reduction (Rh(III) f Rh(I)) at the potential range -0.42 to -0.98 V vs SCE, followed by ligand-based redox couple(s). These novel complexes show effective catalytic properties for the electrocatalytic reduction of carbon dioxide in the potential range -1.26 to -1.44 V.

Removal of color and reduction of chemical oxygen demand (COD) in an industrial azo dye effluent containing chiefly reactive dyes were investigated under single-pass conditions at a dimensionally stable anode (DSA) in a thin electrochemical flow reactor at different current densities, flow rates, and dilutions. With 50% diluted effluent, decolorization was achieved up to 85-99% at 10-40 mA/ cm2 at 5 mL/min flow rate and 50-88% at 30-40 mA/ cm2 at high (10-15 mL/min) flow rates. The COD reduction was maximum (81%) at 39.9 mA/cm2 or above when solution-electrode contact time (Ct) was as high as 21.7 s/cm2 and decreased as Ct declined at a given current density. Cyclic voltammetric studies suggesting an indirect oxidation of dye molecules over the anode surface were carried out at a glassy carbon electrode. The effect of pH on decolorization and COD reduction was determined. An electrochemical mechanism mediated by OCl- operating in the decolorization and COD reduction processes was suggested. The effluent was further treated with NaOCI. The oxidized products from the treated effluents were isolated and confirmed to be free from chlorine-substituted products by IR spectroscopy. From the apparent pseudo-first-order rate data, the second-order rate coefficients were evaluated to be 2.9 M(-1) s(-1) at 5 mL/ min, 76.2 M(-1) s(-1) at 10 mL/min, and 156.1 M(-1) s(-1) at 15 mL/ min for color removal, and 1.19 M(-1) s(-1) at 5 mL/min, 1.79 M(-1) s(-1) at 10 mL/min, and 3.57 M(-1) s(-1) at 15 mL/min for COD reduction. Field studies were also carried out with a pilot-scale cell at the source of effluent generation of different plants corresponding to the industry. Decolorization was achieved to about 94-99% with azo dye effluents at 0.7-1.0 L/min flow costing around Indian Rupees 0.02-0.04 per liter, and to about 54-75% in other related effluents at 0.3-1.0 L/min flow under single-pass conditions.

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