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Acid-catalyzed Hydrolysis of the cis-[Cr(1,10-phenanthroline)2(O2CO)]+ Ion Studied by the u.v.–vis Stopped Flow Method

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Abstract

The cis-[Cr(phen)2(O2CO)]+ ion was prepared through the displacement of two molecules of water from the cis-[Cr(phen)2(OH2)2]3+ by the bidentate carbonate anion. It underwent two-phase hydrolysis reactions under acidic conditions (0.1 < [H+] < 2.7 m) at 5, 10, 15, 20 and 25 °C. Via slow carbonato chelate ring opening (first step k slow1 ) and a second fast decarboxylation(k fast2 value). The first step was preceded by protonation of the coordinate bidentate carbonate ligand. The second step exhibited no pH dependence, while k slow1 values increased with acid concentration that suggested the presence of both protonated and deprotonated reactant species. Based on these observations we have proposed a hydrolysis mechanism featuring H2O-induced ring-opening of the coordinate CO 2−3 group in the first step k slow1 followed by loss of CO 2−3 from two intermediates, [Cr(phen)2(O2COH)]2+ (k slow1 ) and [Cr(phen)2(OH2)(O2COH)]2+ (k fast2 ).

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Authors and Affiliations

  1. Department of Chemistry, University of Gdańsk, Sobieskiego 18/19, Gdańsk, 80-952, Poland

    Dagmara Jacewicz, Aleksandra Dąbrowska, Agnieszka Łapińska & Lech Chmurzyński

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  1. Dagmara Jacewicz
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  2. Aleksandra Dąbrowska
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  3. Agnieszka Łapińska
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  4. Lech Chmurzyński
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Correspondence to Lech Chmurzyński.

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Jacewicz, D., Dąbrowska, A., Łapińska, A. et al. Acid-catalyzed Hydrolysis of the cis-[Cr(1,10-phenanthroline)2(O2CO)]+ Ion Studied by the u.v.–vis Stopped Flow Method. Transition Met Chem 31, 575–579 (2006). https://doi.org/10.1007/s11243-006-0030-4

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