Synthesis and Characterization of<i>trans</i>[CoCl<sub>2</sub>(232N<sub>4</sub><i>x</i>)]<sup>+</sup>(232N<sub>4</sub><i>x</i>= 1,4,8,11Tetraazacyclopentadecane, -cyclohexadecane, -cycloheptadecane, -cyclooctadecane, -cyclononadecane, -cycloicosane, -cyclohenicosane, and -cyclotricosane)
作者:Masanobu Tsuchimoto、Yasuhiro Ito、Junnosuke Fujita
DOI:10.1246/bcsj.68.866
日期:1995.3
Five new macrocyclic ligands which form a large (10—15) chelate ring upon coordination (1,4,8,11-tetraazacyclooctadecane(232N410), -cyclononadecane(232N411), -cycloicosane (232N412), -cyclohenicosane(232N413), and -cyclotricosane(232N415)), and the Co(III) complexes, trans-[CoCl2(232N4x)]+ (x = 7—13, 15) were prepared and characterized. Of six isomers arising from the combination of four chiral nitrogen donor atoms in this type of complex, three and two isomers were obtained, respectively, for complexes with x = 7 and 8, and x = 9—13 and 15. The ligand field parameter of the nitrogen donor atom (Δ(N)) of 232N4x decreases largely from x = 6 to 7, and then shows a small fluctuation with a small decrease at x = even-numbers and a small increase at x = odd-numbers, while a smaller change is observed for the parameter of the chloride ion (Δ(Cl)). The reduction potential for the Co(III)/Co(II) couple (E1/2) shifts to the positive side from the complex with x = 6 to those with x = 7 and 8, and then shows a small change depending on the ring members. The ΔEp(Epa − Epc) values of complexes with x = 8—11 are large, indicating an instability of the medium-sized chelate Co(II) complexes.
五种新的大环配体(1,4,8,11-tetraazacyclooctadecane(232N410), -cyclononadecane(232N411)、(232N410)、-环十一烷(232N411)、-环二十烷(232N412)、-环二十三烷(232N413)和-环三萜(232N415))以及 Co(III) 复合物反式-[CoCl2(232N4x)]+ (x = 7-13, 15)的制备和表征。这类配合物中四个手性氮供体原子的组合产生了六种异构体,其中 x = 7 和 8、x = 9-13 和 15 的配合物分别得到了三种和两种异构体。232N4x 的氮供体原子配体场参数(Δ(N))从 x = 6 到 7 时大幅度下降,然后出现小幅波动,x = 偶数时小幅下降,x = 奇数时小幅上升,而氯离子参数(Δ(Cl))的变化较小。从 x = 6 的复合物到 x = 7 和 8 的复合物,Co(III)/Co(II)偶联物的还原电位(E1/2)向正侧移动,然后根据环成员的不同而发生微小变化。x = 8-11 的配合物的ΔEp(Epa - Epc)值较大,表明中等大小的螯合 Co(II) 配合物不稳定。