Multiple-Path Dissociation Mechanism for Mono- and Dinuclear Tris(hydroxamato)iron(III) Complexes with Dihydroxamic Acid Ligands in Aqueous Solution
作者:Hakim Boukhalfa、Alvin L. Crumbliss
DOI:10.1021/ic0001659
日期:2000.9.18
mono- and dinuclear complexes with Fe(III) in aqueous solution. At conditions where the formation of Fe2(Ln)3 is favored, complexes with each of the two ligand systems undergo [H+]-induced ligand dissociation processes via multiple sequential and parallel paths, some of which are common and some of which are different for the two ligands. The pH jump induced ligand dissociation proceeds in two major
线性合成二异羟肟酸([CH3N(OH)C = O)] 2(CH2)n; 具有短(n = 2)和长(n = 8)烃连接链的H2Ln)与Fe(III)在水溶液中形成单核和双核配合物。在有利于形成Fe2(Ln)3的条件下,与两个配体体系中的每一个的络合物都通过多个连续和平行的路径经历[H +]诱导的配体解离过程,其中一些是常见的,而某些对于两个配体。pH跃迁诱导的配体解离过程分为两个主要阶段(I和II),其中每个阶段均显示为包含多个组分(Ix,其中L2和L8的x = 1-3,IIy,其中y = 1-3对于L2,y = 1-4(对于L8)。提出了一种与动力学和独立ESI-MS数据一致的反应方案,其中包括tris-螯合配合物(为清楚起见,省略了配位的H2O)(Fe2(Ln)3,Fe2(L2)2(L2H)2,Fe(LnH)3 ,Fe(L8)(L8H)),双螯合物(Fe2(Ln)2(2 +),Fe(LnH)2