Structural Study on Alkali‐Carboxylate Functionalized Late‐Transition Metal Bis(dithiocarbamate) Complexes

Phil Liebing, Vreni Behling, Juliane Witzorke
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Abstract

Lithium, sodium, and potassium derivatives of amino‐acid derived bis(dithiocarbamate) complexes of bivalent nickel, palladium, platinum, and copper are readily available by treatment of the carboxylic‐acid functionalized complexes with the respective alkali metal hydroxide. Representative derivatives of the types A4[M(L1)2], A2[M(HL1)2], A[M(HL1)(H2L1)] (N‐dithioato‐iminodiacetate, L1), and A2[M(L2,3)2] (N‐dithioato‐l‐prolinate, L2, and ‐N‐benzylglycinate, L3; A = Li, Na, K; M = Ni, Pd, Pt, Cu) were isolated and characterized by spectroscopic and thermal methods. Six entries were accessible to single‐crystal X‐ray structure determination, revealing the presence of different coordination‐polymeric structures and hydrogen‐bonded assemblies comprising solvent‐separated cations in the solid state. While the transition metal always retains its all‐sulfur coordination with defined geometry, the alkali metals are structurally more flexible. The latter are usually coordinated by carboxylate and water, but additional interactions with sulfur donors are also relevant in some cases.
碱羧酸官能化晚期过渡金属双(二硫代氨基甲酸酯)配合物的结构研究
通过用相应的碱金属氢氧化物处理羧酸官能化络合物,可以很容易地获得镍、钯、铂和铜的二价氨基酸衍生双(二硫代氨基甲酸酯)络合物的锂、钠和钾衍生物。我们分离出了 A4[M(L1)2]、A2[M(HL1)2]、A[M(HL1)(H2L1)](N-二硫代亚氨基二乙酸酯,L1)和 A2[M(L2,3)2](N-二硫代-l-脯氨酸,L2 和-N-苄基甘氨酸,L3;A = Li、Na、K;M = Ni、Pd、Pt、Cu)等类型的代表性衍生物,并通过光谱和热学方法对其进行了表征。其中六种化合物可以进行单晶 X 射线结构测定,揭示出固态中存在不同的配位聚合物结构和氢键集合体,其中包括溶剂分离的阳离子。过渡金属始终保持全硫配位,并具有确定的几何形状,而碱金属的结构则更为灵活。后者通常由羧酸盐和水配位,但在某些情况下也会与硫供体发生额外的相互作用。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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