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The Effect of Ammine, Ethanoate, Trichloro- and Trifluoroethanoate Ligands On Tris(2,4-Pentanedionato)Chromium(Iii) Formation in High ph aQueous Solution

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The yields of tris(2,4-pentanedionato)chromium(III) (Cr(acac)3) formed in the presence of either the ammonia (Am), ethanoate (ET), trichloroethanoate (TCE), or trifluoroethanoate (TFE) ligand in high pH aqueous solution, were compared with those from a medium containing only hydroxyl and water as the principal ligands besides the acac. The presence of Am, ET, and TCE drastically reduced the yields at pH's 9.5-10.5, 7.5-9.0/9.5-110,and 9.0-12.0, respectively in increasing order ET < Am < TCE. The role of Am is attributed mainly to the oxo-bridged species ((OH)m.(H2O)nAm5-(.1.)Cr(O)(OH)CrAm5-(m+n)(H2O)n(OH)m)3-2m (1), ((OH)m(H2O)nAm5-(m+n)Cr(O)2CrAm5-(m+n)(H2O)n(OH)m )2-2m (2), and ((OH)m(H2O)nAm5-(m+n)Cr(O)(OH)CrAm4(m+n)(H2O)n(OH)m+r)2-2m (3). 2 is the most deactivating species mainly on the basis that the Cr-O bond of the oxo-bridge is suggested as being stronger than the Cr-O bond of the hydroxobridge. As for ET and TCE, oxo-bridged polymeric ethanoato- and trichloroethanoatochromium(III) species are also proposed as the main origin of the drastic deactivation of the reaction not observed for TFE due possibly, to the insignificance of oxo-bridges in trifluoroethanoatochromium(III) species.

Affiliations: 1: Inorganic Research Laboratory, Department of Chemistry Makerere University P.O. Box 7062, Kampala, Uganda


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