{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,16]],"date-time":"2025-10-16T00:57:00Z","timestamp":1760576220583,"version":"build-2065373602"},"reference-count":47,"publisher":"Wiley","issue":"2","license":[{"start":{"date-parts":[[2009,2,9]],"date-time":"2009-02-09T00:00:00Z","timestamp":1234137600000},"content-version":"vor","delay-in-days":39,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Electrophoresis"],"published-print":{"date-parts":[[2009,1]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Enantiomerization of octahedral tris(<jats:italic>\u03b1<\/jats:italic>\u2010diimine)\u2013transition metal complexes was investigated by enantioselective dynamic MEKC. Varying both the transition metal ion (Fe<jats:sup>2+<\/jats:sup>, Fe<jats:sup>3+<\/jats:sup>, and Ni<jats:sup>2+<\/jats:sup>) and the bidentate diimine ligand (1,10\u2010phenanthroline and 2,2\u2032\u2010bipyridyl), the enantiomer separations were performed either in a 100\u2009mM sodium tetraborate buffer (pH 9.3) or in a 100\u2009mM sodium tetraborate\/sodium dihydrogenphosphate buffer (pH 8.0) both containing sodium cholate as chiral surfactant. The unified equation of dynamic chromatography was employed to determine apparent reaction rate constants from the electropherograms showing distinct plateau formation. Apparent activation parameters \u0394<jats:italic>H<\/jats:italic><jats:sup>\u2021<\/jats:sup> and \u0394<jats:italic>S<\/jats:italic><jats:sup>\u2021<\/jats:sup> were calculated from temperature\u2010dependent measurements between 10.0 and 35.0\u00b0C in 2.5\u2009K steps. It was found that the nature of the central metal ion and the ligand strongly influence the enantiomerization barrier. Surprisingly, complexes containing the 2,2\u2032\u2010bipyridyl ligand show highly negative activation entropies between \u2212103 and \u2212116\u2009J (K\u2009mol)<jats:sup>\u22121<\/jats:sup> while the activation entropy of tris(1,10\u2010phenanthroline) complexes is positive indicating a different mechanism of interconversion. Furthermore, it was found that the Ni<jats:sup>2+<\/jats:sup> complexes are stereostable under the conditions investigated here making them a lucent target as enantioselective catalysts.<\/jats:p>","DOI":"10.1002\/elps.200800320","type":"journal-article","created":{"date-parts":[[2009,2,9]],"date-time":"2009-02-09T09:32:20Z","timestamp":1234171940000},"page":"329-336","source":"Crossref","is-referenced-by-count":7,"title":["Investigation of the stereodynamics of tris\u2010(<i>\u03b1<\/i>\u2010diimine)\u2013transition metal complexes by enantioselective dynamic MEKC"],"prefix":"10.1002","volume":"30","author":[{"given":"Sabrina","family":"Bremer","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Oliver","family":"Trapp","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2009,2,9]]},"reference":[{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1002\/elps.200600411"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1002\/elps.200700070"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1002\/elps.200406173"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1002\/elps.200405928"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1522-2683(19990901)20:13<2605::AID-ELPS2605>3.0.CO;2-M"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0021-9673(99)01168-1"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.aca.2005.04.027"},{"key":"e_1_2_6_9_2","doi-asserted-by":"publisher","DOI":"10.1002\/chir.1052"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0021-9673(03)00238-3"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1039\/b502508g"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1002\/jssc.200600129"},{"key":"e_1_2_6_13_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0021-9673(01)93677-5"},{"key":"e_1_2_6_14_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19911030117"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199100741"},{"key":"e_1_2_6_16_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00028a020"},{"key":"e_1_2_6_17_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo981885o"},{"key":"e_1_2_6_18_2","volume":"947","author":"Hochmuth D. 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