spectrophotometry in acetonitrile. The kinetics for the formation of NiII/HL 1:1 adducts was studied by stopped-flow techniques, which showed that the process followed a two-consecutive mechanism. Experimental evidence and theoretical calculations indicated the formation of an unidentate intermediate in the first step, according to a dissociative interchange mechanism. Ring-closure occurs in the second step and
NiII 阳离子与双齿席夫碱
配体、N-烷基-5-X-
水杨醛亚胺 HL(X = H;R = Et、nPr、tBu;X = Cl、OMe、
NO2;R = nPr)和双(通过紫外/可见分光光度法研究 Nn-烷基-5-X-
水杨醛亚
氨基)
镍(II)配合物 [Ni
L2](X = H;R = Et、nPr、nBu;X = Cl、OMe、Me;R = nPr)在
乙腈中。NiIII/HL 1:1 加合物的形成动力学通过停流技术进行研究,表明该过程遵循两个连续的机制。根据解离交换机制,实验证据和理论计算表明在第一步中形成了无齿中间体。闭环发生在第二步,对于吸电子取代的席夫碱,其速度较慢。
镍 (II) 阳离子与 [Ni
L2] 相互作用,提供 [NiL]+ 和 [Ni2L3]+ 物质;发现相关的平衡常数与 5-X
配体取代基的电子效应有关。(© Wiley-
VCH Verlag GmbH, 69451 Weinheim