PubMed · 10683031
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M del Pilar Bernal, K Loftfield, J D Nussdorf. 2000-02-12. Taxane-induced glaucoma.. https://doi.org/10.1016/s0140-6736(05)73228-1
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The inclusion behavior of methylviologen (N,N'-dimethyl-4,4'-bipyridinium, MV) dication in cucurbit[7]uril (CB[7]) has been studied by using various spectroscopic and electrochemical methods. The inclusion complex of MV dication in CB[7] is stable thermodynamically and kinetically. The electrochemical study reveals that unlike beta-cyclodextrin, CB[7] prefers the charged species, MV dication (MV(2+)), and cation radical (MV(+)*) to the fully reduced neutral (MV(0) species as guests. Dimerization of MV(+)* is suppressed effectively by forming a stable complex with CB[7] in aqueous solution as confirmed by spectroelectrochemical experiments. Furthermore, the first redox process (MV(2+)/MV(+)*) of the MV(2+)-CB[7] complex occurs predominantly via the direct electron transfer pathway, whereas the second redox process (MV(+)*/MV(0)) occurs via both the direct and indirect pathway because of the low affinity of the fully reduced species MV(0) to CB[7].
Two new terpyridine dimanganese oxo complexes [Mn(2)(III,IV)(mu-O)(2)(terpy)(2)(CF(3)CO(2))(2)](+) (3) and [Mn(2)(III,III)(mu-O)(terpy)(2)(CF(3)CO(2))(4)] (4) (terpy = 2,2':6,2' '-terpyridine) have been synthesized and their X-ray structures determined. In contrast to the corresponding mixed-valent aqua complex [Mn(2)(III,IV)(mu-O)(2)(terpy)(2)(H(2)O)(2)](3+) (1), the two Mn atoms in 3 are not crystallographically equivalent. The neutral binuclear monooxo manganese(III,III) complex 4 exhibits two crystallographic forms having cis and trans configurations. In the cis complex, the two CF(3)CO(2)(-) ligands on each manganese adopt a cis geometry to each other; one CF(3)CO(2)(-) is trans to the oxygen of the oxo bridge while the second is cis. In the trans complex, the two coordinated CF(3)CO(2)(-) have a trans geometry to each other and are cis to the oxo bridge. The electrochemical behavior of 3 in organic medium (CH(3)CN) shows that this complex could be oxidized into its corresponding stable manganese(IV,IV) species while its reduced form manganese(III,III) is very unstable and leads by a disproportionation process to Mn(II) and Mn(IV) complexes. Complex 4 is only stable in the solid state, and it disproportionates spontaneously in CH(3)CN solution into the mixed-valent complex 3 and the mononuclear complex [Mn(II)(terpy)(2)](2+) (2), thereby preventing the observation of its electrochemical behavior.
The first deliberate syntheses of molecules in which pairs of quadruply bonded Mo2 units are bridged by N,N'-diarylterephthaloyldiamidate (aryl = Ph, m-CF3Ph) ligands are described. The addition of neutral N,N'-diarylterephthaloyldiamide to 2 equiv of [Mo2(DAniF)3(MeCN)2]+ (DAniF = N,N'-di-p-anisylformamidinate) followed by the introduction of excess H3CO- in MeCN results in the formation of (DAniF)3Mo2[(C6H5)NC(O)C6H4(O)CN(C6H5)]Mo2(DAniF)3 (1) and (DAniF)3Mo2[[(m-CF3)C6H5]NC(O)C6H4(O)CN[(m-CF3)C6H5]]Mo2(DAniF)3 (2). The DeltaE1/2 for the oxidation of each Mo2 unit is greater for these terephthaloyldiamidate-bridged molecules (approximately 100 mV) than for the analogous terephthalate-bridged compound (approximately 60 mV). Variation in the nature of the substituents on the diamidate nitrogen atoms offers a means to fine-tune the oxidation potentials of the Mo2 units.