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Comparison of these results for M(PS) complexes with those known for the parent M(PO) phosphate species, where PO<\/jats:italic>2\u2212<\/jats:italic><\/jats:sup>=CH<\/jats:italic>3<\/jats:italic><\/jats:sub>OPO<\/jats:italic>${_{3}^{2-}}$<\/jats:styled-content> or UMP<\/jats:italic>2\u2212<\/jats:italic><\/jats:sup> (uridine 5\u2032\u2010monophosphate), shows that the alkaline earth metal ions, as well as Mn<\/jats:italic>2+<\/jats:italic><\/jats:sup>, Co<\/jats:italic>2+<\/jats:italic><\/jats:sup>, and Ni<\/jats:italic>2+<\/jats:italic><\/jats:sup> have a higher affinity for phosphate groups than for their thio analogues. However, based on the linear log\u2009<\/jats:italic>K${_{{\\rm M}({\\rm R} \\char45 {\\rm PO}_{3})}^{{\\rm M}}}$<\/jats:styled-content> versus p<\/jats:italic>K${_{{\\rm H}({\\rm R} \\char45 {\\rm PO}_{3})}^{{\\rm H}}}$<\/jats:styled-content> relationships (R\u2010PO<\/jats:italic>${_{3}^{2-}}$<\/jats:styled-content>=simple phosphate monoester or phosphonate ligands with a non\u2010interacting residue R) it becomes clear that the indicated observation is only the result of the lower basicity of the thiophosphate residue. In contrast, the thio complexes of Zn<\/jats:italic>2+<\/jats:italic><\/jats:sup> and Cd<\/jats:italic>2+<\/jats:italic><\/jats:sup> are more stable than their parent phosphate ones, and this despite the lower basicity of the PS<\/jats:italic>2\u2212<\/jats:italic><\/jats:sup> ligands. This stability increase is identical for M(MeOPS) and M(UMPS) species and amounts to about 0.6 and 2.4 log units for Zn(PS) and Cd(PS), respectively. Since no other binding site is available in MeOPS<\/jats:italic>2\u2212<\/jats:italic><\/jats:sup>, this enhanced stability has to be attributed to the S atom. Indeed, from the mentioned stability differences it follows that Cd<\/jats:italic>2+<\/jats:italic><\/jats:sup> in Cd(PS) is coordinated by more than 99% to the thiophosphate S atom; the same value holds for Pb(PS), which was studied earlier. The formation degree of the Sbonded isomer amounts to 76\u00b16\u2009% for Zn(PS) and is close to zero for the corresponding Mg<\/jats:italic>2+<\/jats:italic><\/jats:sup>, Ca<\/jats:italic>2+<\/jats:italic><\/jats:sup>, and Mn<\/jats:italic>2+<\/jats:italic><\/jats:sup> species. It is further shown that Zn(MeOPS)(aq)<\/jats:italic>2+<\/jats:italic><\/jats:sup> releases a proton from a coordinated water molecule with p<\/jats:italic>Ka<\/jats:italic><\/jats:sub>\u22486.9; i.e., this deprotonation occurs at a lower pH value than that for the same reaction in Zn(aq)<\/jats:italic>2+<\/jats:italic><\/jats:sup>. Since Mg<\/jats:italic>2+<\/jats:italic><\/jats:sup>, Ca<\/jats:italic>2+<\/jats:italic><\/jats:sup>, Mn<\/jats:italic>2+<\/jats:italic><\/jats:sup>, and Cd<\/jats:italic>2+<\/jats:italic><\/jats:sup> have a relatively low tendency for hydroxo complex formation, it was possible, for these M<\/jats:italic>2+<\/jats:italic><\/jats:sup>, to also quantify the stability of the binuclear complexes, M<\/jats:italic>2<\/jats:italic><\/jats:sub>(UMPS\u2212H)<\/jats:italic>+<\/jats:italic><\/jats:sup>, where one M<\/jats:italic>2+<\/jats:italic><\/jats:sup> is thiophosphate\u2010coordinated and the other is coordinated at (N3)<\/jats:italic>\u2212<\/jats:italic><\/jats:sup> of the uracil residue. The impact of the results presented herein regarding M<\/jats:italic>2+<\/jats:italic><\/jats:sup>\/nucleic acid interactions, including those of ribozymes (rescue experiments), is briefly discussed.<\/jats:italic><\/jats:p>","DOI":"10.1002\/cbic.200200551","type":"journal-article","created":{"date-parts":[[2003,7,3]],"date-time":"2003-07-03T12:03:56Z","timestamp":1057233836000},"page":"593-602","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":29,"title":["Complex Formation of Divalent Metal Ions with Uridine 5\u2032\u2010O<\/i>\u2010Thiomonophosphate or Methyl Thiophosphate: Comparison of Complex Stabilities with Those of the Parent Phosphate Ligands"],"prefix":"10.1002","volume":"4","author":[{"given":"Carla P.","family":"Da Costa","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Andrzej","family":"Okruszek","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Helmut","family":"Sigel","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2003,6,27]]},"reference":[{"key":"e_1_2_7_1_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja962970l"},{"key":"e_1_2_7_2_2","doi-asserted-by":"publisher","DOI":"10.1351\/pac199971091727"},{"key":"e_1_2_7_3_2","doi-asserted-by":"publisher","DOI":"10.1007\/s00775-001-0316-0"},{"key":"e_1_2_7_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00970a054"},{"key":"e_1_2_7_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/bi00317a026"},{"key":"e_1_2_7_6_2","unstructured":"\u00a0"},{"key":"e_1_2_7_7_2","doi-asserted-by":"publisher","DOI":"10.1146\/annurev.bi.49.070180.004305"},{"key":"e_1_2_7_8_2","doi-asserted-by":"publisher","DOI":"10.1146\/annurev.bi.54.070185.002055"},{"key":"e_1_2_7_9_2","unstructured":"\u00a0"},{"key":"e_1_2_7_10_2","first-page":"1","volume":"32","author":"Klevickis C.","year":"1996","journal-title":"Met. 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