Acid aquation with kaq= 1.66 × 104 s–1 at 50 °C is quite slow. The CuII and octahedral NiII complexes are labile in acidic solution, unlike the complexes of 1,4,8,11-tetra-azacyclotetradecane. The kinetics of the acid-catalysed dissociation have been studied in detail. For both complexes rate =kH[complex][H +]2, indicating the involvement of two protons in the transition state of the reaction. For
描述了标题五齿大环
配体L的制备。制备并表征了配合物[NiL(OH 2)] [ClO 4 ] 2,[CuL] [ClO 4 ] 2和[CoLCl] [ClO 4 ] 2。由于两个手性氮中心,络合物可以具有三种可能的构型。有两个N-内消旋非对映异构体和一个N-外消旋非对映异构体。碳13 nmr测量表明,Co III配合物是可能的立体异构体的混合物。[COLCl] 2+的碱
水解相当迅速,k OH = 2.45×10 4dm 3 mol –1 s –1在30°C且I = 0.1 mol dm –3,可以根据mer -N 3供体组进行合理化。在50°C时,k aq = 1.66×10 4 s –1的酸化过程非常缓慢。与
1,4,8,11-四氮杂环十四烷的络合物不同,Cu II和八面体Ni II络合物在酸性溶液中不稳定。已经详细研究了酸催化离解的动力学。对于两个复合物,速率= k H [复合物] [H +