摘要
用定量体积排除色谱方法研究了过渡金属Fe(Ⅲ)、Co(Ⅲ)、Cu(Ⅱ)、Ni(Ⅱ)的乙酰丙酮螯合物在四氢呋喃溶液中的加合和缔合行为。在溶液中乙酰丙酮钴(Ⅲ)以单个螯合物分子的形式存在,乙酰丙酮铜(Ⅱ)和乙酰丙酮铁(Ⅲ)与溶剂加合生成加合物,乙酰丙酮铁(Ⅲ)除加合物外还存在缔合度为2-10的多分散缔合物,乙酰丙酮镍(Ⅱ)水合物在四氢呋喃中产生了加合交换作用,同时存在缔合度为6左右的缔合物。色谱数据给出了螯合物。
The self-association and adduct formation of the transition metal chelates, viz, iron(Ⅲ). cobalt(Ⅲ), copper(Ⅱ), nickel(Ⅱ) of acetylacetone in tetrahydrofurane were investigated with the aid of quantitative size exclusion chromatography. Tris (acetylacetonato) cobalt(Ⅲ) in thesolution exists in the form of a single chelate molecule. Bis(acetylacetonato) copper(Ⅱ) and Tris (acetylacetonato) iron(Ⅲ) react with the solvent to form adducts. Tris (acetylacetonato) iron(Ⅲ) in tetrahydrofurane also self-associated to form a polydisperse aggregate with association number from 2 to 10. Addition ligand exchanging occured in tetrahydrofurane for bis(acetylacetonato) nickel(Ⅱ) hydrate and a small amount of aggregate with association number around 6 is also present. The relative contents of the chelate, adduct and aggregate are evaluated from the chromatographic data. The refractive index increments of the chelates and that of the coordinated metals are determined from the R.I. detecting response constants of the chelates in the elucnt. Both the refractive index increments of the coordinated metals and the lag of the chromatographic retention values of the chelates increase in the order of Ni, Cu, Co, Fe, which is the same as that of the first ionization energies of the transition metals.
出处
《无机化学学报》
SCIE
CAS
CSCD
北大核心
1990年第2期215-216,共2页
Chinese Journal of Inorganic Chemistry
基金
国家自然科学基金
关键词
乙酰丙酮
螯合物
体积排除色谱
镍
size exciusion chromatography chelates of acetylacetone adduct self-association refractive index incremeat
