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Synthesis and characterization of rhodium complexes containing 2,4,6-tris(2-pyridyl)-1,3,5-triazine and its metal-promoted hydrolytic products: Potential uses of the new complexes in electrocatalytic reduction of carbon dioxide

Journal Article · · Inorganic Chemistry
DOI:https://doi.org/10.1021/ic9709739· OSTI ID:316203
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  1. Central Salt and Marine Chemicals Research Inst., Bhavnagar (India)
The reaction of 2,4,6-tris(2-pyridyl)-1,3,5-triazine (tptz) with RhCl{sub 3} {center_dot} 3H{sub 2}O has been studied under different experimental conditions. This reaction in ethanol resulted in the formation of [Rh(tptz)Cl{sub 3}]{center_dot}2H{sub 2}O (1), whereas the bis-chelate complex [Rh(tptz){sub 2}][ClO{sub 4}]{sub 3}{center_dot}2H{sub 2}O (2) was obtained in a two-step reaction in acetone; the chlorides from RhCl{sub 3} were removed in the first step using AgClO{sub 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{sub 6}]{center_dot}H{sub 2}O (3) and [Rh(bpca){sub 2}][ClO{sub 4}] (6), respectively. A mixed-ligand complex, [Rh(bpca)(tpy)][PF{sub 6}]{sub 2}{center_dot}CH{sub 3}CN (4), was obtained by the reaction of either 1 with tpy or [Rh(tpy)Cl{sub 3}] (5) with tptz in ethanol-water medium. The crystal structures of complexes 1 and 4 have been determined. These novel complexes show effective catalytic properties for the electrocatalytic reduction of carbon dioxide in the potential range {minus}1.26 to {minus}1.44 V.
OSTI ID:
316203
Journal Information:
Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 22 Vol. 37; ISSN 0020-1669; ISSN INOCAJ
Country of Publication:
United States
Language:
English