{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T21:11:45Z","timestamp":1760303505531,"version":"build-2065373602"},"reference-count":61,"publisher":"Wiley","issue":"9","license":[{"start":{"date-parts":[[2005,2,25]],"date-time":"2005-02-25T00:00:00Z","timestamp":1109289600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2005,4,22]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>While the thermochemical stability of gas\u2010phase HgF<jats:sub>4<\/jats:sub> against F<jats:sub>2<\/jats:sub> elimination was predicted by accurate quantum chemical calculations more than a decade ago, experimental verification of \u201ctruly transition\u2010metal\u201d mercury(<jats:sc>IV<\/jats:sc>) chemistry is still lacking. This work uses detailed density functional calculations to explore alternative species that might provide access to condensed\u2010phase Hg<jats:sup>IV<\/jats:sup> chemistry. The structures and thermochemical stabilities of complexes Hg<jats:sup>IV<\/jats:sup>X<jats:sub>4<\/jats:sub> and Hg<jats:sup>IV<\/jats:sup>F<jats:sub>2<\/jats:sub>X<jats:sub>2<\/jats:sub> (X<jats:sup>\u2212<\/jats:sup>=AlF<jats:sub>4<\/jats:sub><jats:sup>\u2212<\/jats:sup>, Al<jats:sub>2<\/jats:sub>F<jats:sub>7<\/jats:sub><jats:sup>\u2212<\/jats:sup>, AsF<jats:sub>6<\/jats:sub><jats:sup>\u2212<\/jats:sup>, SbF<jats:sub>6<\/jats:sub><jats:sup>\u2212<\/jats:sup>, As<jats:sub>2<\/jats:sub>F<jats:sub>11<\/jats:sub><jats:sup>\u2212<\/jats:sup>, Sb<jats:sub>2<\/jats:sub>F<jats:sub>11<\/jats:sub><jats:sup>\u2212<\/jats:sup>, OSeF<jats:sub>5<\/jats:sub><jats:sup>\u2212<\/jats:sup>, OTeF<jats:sub>5<\/jats:sub><jats:sup>\u2212<\/jats:sup>) have been assessed and are compared with each other, with smaller gas\u2010phase HgX<jats:sub>4<\/jats:sub> complexes, and with known related noble gas compounds. Most species eliminate F<jats:sub>2<\/jats:sub> exothermically, with energies ranging from only about \u221260 kJ\u2009mol<jats:sup>\u22121<\/jats:sup> to appreciable \u2212180 kJ\u2009mol<jats:sup>\u22121<\/jats:sup>. The lower stability of these species compared to gas\u2010phase HgF<jats:sub>4<\/jats:sub> is due to relatively high coordination numbers of six in the resulting Hg<jats:sup>II<\/jats:sup> complexes that stabilize the elimination products. Complexes with AsF<jats:sub>6<\/jats:sub> ligands appear more promising than their SbF<jats:sub>6<\/jats:sub> analogues, due to differential aggregation effects in the Hg<jats:sup>II<\/jats:sup> and Hg<jats:sup>IV<\/jats:sup> states. HgF<jats:sub>2<\/jats:sub>X<jats:sub>2<\/jats:sub> complexes with X<jats:sup>\u2212<\/jats:sup>=OSeF<jats:sub>5<\/jats:sub><jats:sup>\u2212<\/jats:sup> or OTeF<jats:sub>5<\/jats:sub><jats:sup>\u2212<\/jats:sup> exhibit endothermic fluorine elimination and relatively weak interactions in the Hg<jats:sup>II<\/jats:sup> products. However, elimination of the peroxidic (OEF<jats:sub>5<\/jats:sub>)<jats:sub>2<\/jats:sub> coupling products of these ligands provides an alternative exothermic elimination pathway with energies between \u2212120 and \u2212130 kJ\u2009mol<jats:sup>\u22121<\/jats:sup>. While all of the complexes investigated here thus have one exothermic decomposition channel, there is indirect evidence that the reactions should exhibit nonnegligible activation barriers. A number of possible synthetic pathways towards the most interesting condensed\u2010phase Hg<jats:sup>IV<\/jats:sup> target complexes are proposed.<\/jats:p>","DOI":"10.1002\/chem.200401130","type":"journal-article","created":{"date-parts":[[2005,2,25]],"date-time":"2005-02-25T13:27:39Z","timestamp":1109338059000},"page":"2743-2755","source":"Crossref","is-referenced-by-count":36,"title":["Can Weakly Coordinating Anions Stabilize Mercury in Its Oxidation State +<scp>IV<\/scp>?"],"prefix":"10.1002","volume":"11","author":[{"given":"Sebastian","family":"Riedel","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Michal","family":"Straka","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Martin","family":"Kaupp","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2005,4,15]]},"reference":[{"key":"e_1_2_8_1_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic00088a012"},{"key":"e_1_2_8_2_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.473437"},{"key":"e_1_2_8_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00430a020"},{"key":"e_1_2_8_4_2","unstructured":"Indeed the EPR data reported[3]for [HgIII(cyclam)]3+do not look much like one would expect for a 5d9complex."},{"key":"e_1_2_8_5_2","doi-asserted-by":"publisher","DOI":"10.1051\/jcp\/1979760630"},{"key":"e_1_2_8_5_3","doi-asserted-by":"publisher","DOI":"10.1002\/zaac.19865400912"},{"key":"e_1_2_8_6_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19931050639"},{"key":"e_1_2_8_6_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199308611"},{"key":"e_1_2_8_7_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0020-1693(00)83833-5"},{"key":"e_1_2_8_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic00007a044"},{"key":"e_1_2_8_8_3","doi-asserted-by":"publisher","DOI":"10.1021\/ja00200a056"},{"key":"e_1_2_8_8_4","doi-asserted-by":"publisher","DOI":"10.1063\/1.457082"},{"key":"e_1_2_8_9_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0009-2614(99)00147-5"},{"key":"e_1_2_8_10_2","doi-asserted-by":"publisher","DOI":"10.1039\/b315019d"},{"key":"e_1_2_8_11_2","doi-asserted-by":"publisher","DOI":"10.1039\/B203585E"},{"key":"e_1_2_8_12_2","unstructured":"K. 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