作者:D.L. Lewis、R.K. Murmann
DOI:10.1016/0022-1902(63)80415-7
日期:1963.11
of the ligand exchange of [Ni(AO)2-H]+, [Ni(MeAO)2H]+ and [Ni(EnAO)H]+ have been investigated using C14 labeled ligands. It was found that the exchange for the series follows the general law: R = k1[complex]T + k2[complex]T[ligand]F. The overall rates are in the order AO > MeAO ⩾ EnAO. With [Ni(AO)2H]+ the exchange is rapid and carried predominately by the ligand dependent, k2 term. With [Ni(MeAO)2H]+
的配位体交换的动力学[镍(AO)2 -H] +,[镍(MEAO)2 H] +和[镍(EnAO)H] +已用C研究14标记的配体。结果发现,对于该系列中的交换如下的一般规律:- [R = ķ 1 [复杂] Ť + ķ 2 [复杂] Ť [配体] ˚F。总费率按AO> MeAO⩾EnAO的顺序排列。与[镍(AO)2 H] +的交换是快速和由配体依赖性,主要进行ķ 2项。使用[Ni(MeAO)2 [ H] +在恒定的[MeAO] T下,R在pH = 8的区域内显示最小值。在碱性区域,较快的速率是由于游离配体浓度增加,而酸性催化作用是基于一半键合的中间体。对于[Ni(EnAO)H] +,交换由k 1项进行,其中k 2小。依赖于配体的步骤的阶数k 2,是AO> MeAO> EnAO,并且是由于在形成五个坐标激活状态时存在位阻。外来螯合离子或分子对交换的催化作用支持了这一点。将这些结果与与ED