Anaerobic Solid-Phase Thermal Configurational Transformations of Cobalt(II) Complexes.
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New examples of thermal tetrahedral-to-octahedral transformation were discovered and studied in the thermal reactions of disodium tetrakis(aryloxo)cobaltate(II) complexes, of the formula Na2[Co(OAr)4(thf)m]·nthf (OAr = o-chloro-, o-bromo-, m-chloro-, p-bromo-, 2,4-dichloro-, 2,4-dimethyl- or 2,6-dichlorophenoxo; m = 2 for all complexes except for 2,4-dimethylphenoxo complex where m = 0; thf: tetrahydrofuran; n = 1—3), in the solid phase. With one exception, the original complexes were all violet colored and have octahedral configurations. The exception is Na2[Co(2,4-Me2C6H3O)4]·thf, which has an intense blue color and its electronic and magnetic data are characteristic of tetrahedral cobalt(II). The aryloxo complexes of 2,6-dichloro-, m-chloro-, and p-bromophenoxo show a two-step thermochromism, violet → blue → rose, upon heating. These steps correspond to structural changes to tetrahedral thf-free complexes and then to aryloxo bridged polymers with octahedral cobalt(II) ions, respectively. o-Chloro- and o-bromophenoxo complexes underwent only thermal desolvation–polymerization, which occurs in one step, changing directly into the rose aryloxo-bridged polymers. 2,4-Dichlorophenoxo complex shows only one-step thermochromism, violet → blue, thus changing from the octahedral to tetrahedral configuration. The remainder complex, of 2,4-dimethylphenoxo, does not show any color changes and retained its tetrahedral configuration until it decomposed. The reverse changes of the thermal products to the original complexes proceed on standing under dry thf atmosphere, for some hours or days.
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公益社団法人 日本化学会 | 論文
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