SYNTHESIS AND REACTIVITY OF AZA-CAPPED ENCAPSULATED CO(III) IONS
SYNTHESIS AND REACTIVITY OF AZA-CAPPED ENCAPSULATED CO(III) IONS
复制标题
DOI：
10.1021/ja00386a030
复制
发表时间：
1982-01-01
影响因子：
15
通讯作者：
SPRINGBORG, J
中科院分区：
文献类型：
--
作者：
CREASER, II;GEUE, RJ;SPRINGBORG, J
从[Co(En)3]3+(Sep=sePulchrate=1，3，6，8，10，13，16，19-八氮杂双环[6.6.[Co(Sen)]3+(sen=5-甲基-5-(4-氨基-2-氮杂丁基)-3，7-二氮杂环-1，9-二胺)，并报道了其晶体结构。记录了Co(II)-Co(III)氧化态的氧化还原电位、可见光谱、旋转色散、圆二色和磁性，以及笼子的酸碱性质和对酸、碱的稳定性。Co(II)-Co(III)的电子自交换速率非常快(25℃时分别为5.1M~(-1)和2.9M~(-1)·S~(-1))，比[Co(En)_3]~(3+)/2+的电子自交换速率大-105倍。[Co(Sep)]~(2+)从02还原到H~(202)也很快(在25℃时为43M‘~(-1)S~(-1))，并且显然不是通过022“”与两个Co(III)离子结合的途径发生的。这些络合物异常稳定，化学成分也不同寻常
The synthesis of the cage complexes [Co (sep)] 2" 1"''3" 1" from [Co (en) 3] 3+(sep= sepulchrate= 1, 3, 6, 8, 10, 13, 16, 19-octaazabicyclo [6.6. 6] eicosane) and analogous cages from [Co (sen)] 3+(sen= 5-methyl-5-(4-amino-2-azabutyl)-3, 7-diazano-nane-1, 9-diamine) are described, and the crystal structure of [€(8ß)] 8206 20 is reported. The oxidation-reduction potentials, visible spectra, rotary dispersion, circular dichroism, and magnetism of the Co (II)-Co (III) oxidation states are recorded, along with the acid-base properties and stability of the cages toward acids and bases. The Co (II)-Co (III) electron self-exchange rates are unusually fast (5.1 and 2.9 M" 1 s" 1 at 25 C) and— 105-fold greater than that for [Co (en) 3] 3+/2+. The [Co (sep)] 2+ reduction of 02 to H202 is also rapid (43 M'1 s" 1 at 25 C) and apparently occurs by an outer-sphere path rather than through the route that leaves 022"" bound to two Co (III) ions. The complexes are unusually stable, and the chemistry is unusual for