铁系元素冠醚配合物的研究——Ⅱ. 铁系氯化物与4''-碘苯并-15-冠-5固态配合物的合成与性质

对碱金属、希土与苯并-15-冠-5冠醚配合物的研究指出,4′-取代单苯并冠醚的阳离子配合物的稳定性及其他性质,受取代基电子效应的影响,给电性取代基可增加芳醚氧原子上的电子密度,改变冠氧的极性,从而影响其配位能力,扩大希土配合物之间性质上的差别,达到分离的目的。对于铁系元素,文献报导甚少。我们继Ⅰ之后,又合成了三氯化铁水合物与4′-碘苯并-15-冠-5固态配合物,并研究了其性质。     

Oxidation of theexo- andendo-phenylcyclohexadienyl iron complexes Fe(η5-6-PhC6H6) (η5- C5H5)

The roe of oxidatively induced homolyhc scission a the C(sp³)-H bonds in the iron phenykychhexadienyl complexes Fe(⁵-6-PhC₆H₆)(⁵-C₅H₅) (1) depends on the spatial orientation of the Ph substitutent. In the case of the (1 _endo ⁺) radical cation this process, resulting in the cationic biphenyl complex (Fe(⁶ -C₆H₅C₆H₅)(⁵-C₅H₅)]⁺ (2 ⁺), is fast and proceeds for several minutes. In the case of the more stable radical cation (1 _exo ⁺) the formation of 2⁺ is slow and takes tens minutes to complete.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1698–1700, July, 1996.     

Synthesis, structure, and spectroscopy of phenylacetylenylene rods incorporating meso-substituted dipyrrin ligands

The synthesis, structure, and spectroscopic characterization of a series of phenylacetylenylene rodlike molecules containing dipyrromethene (dipyrrin) ligands are described. The combination of the phenylacetylenylene groups with the porphyrinogenic dipyrrin moieties results in a rich absorption spectroscopy for these compounds, although the fluorescence of the phenylacetylenylene moiety is quenched by presence of the dipyrrin chelator. The Cu(2+) and Fe(3+) complexes of these ligands have been prepared and three of these compounds have been structurally characterized by using single-crystal X-ray diffraction. Unlike other octahedral metal-dipyrrin complexes described to date, one of the iron complexes demonstrates ideal threefold symmetry in the solid-state. The elongated structure and high symmetry of these complexes suggests the use of these meso-substituted phenylacetylenylene ligands as an interesting class of extended, branched molecules for the construction of supramolecular architectures.     

Tetrachloroferrate(III)-selective liquid membrane electrode based on crystal violet

An extract of crystal violet-tetrachloroferrate(III) in nitrobenzene was used to prepare a tetrachloroferrate(III)-selective liquid membrane electrode with a poly(vinyl chloride) support. The optimal conditions to determine 2.5 × 10^–5 – 5.0 × 10^–2 M iron(III) as tetrachloroferrate(III) (anionic slope 56 mV/decade, detection limit 7.9 × 10^–6 M) were found to be 4.0–5.5.M total chloride in 0.75–1.5M hydrochloric acid. The electrode was reliably applied to determine iron in human blood, haematite and mineralized vitamin syrup by direct potentiometry, standard and sample additions as well as standard subtraction techniques.     

流动注射光度法同时测定铜基合金中的铝和铁

提出了同时测定铜基合金中铝和铁的流动注射分析法。以０．０４ｍｏｌ／ＬＨＣｌ作载液，铬天青Ｓ为显色剂，通过测定６２８ｎｍ处铝、铁两配合物的吸光度之和及铝配合物的吸光度，实现了两组分的同时测定。在优化的实验条件下，检测限：Ａｌ和Ｆｅ分别为１．６９×１０－３和１．７３×１０－３ｍｇ／Ｌ，Ａｌ浓度在０～０．８ｍｇ／Ｌ；Ｆｅ浓度在０～１．０ｍｇ／Ｌ时服从比耳定律。进样频率为６０样／ｈ，所拟方法用于实际样品分析，获得满意结果。     

比值光谱导数法同时测定铝合金中铁,铜,锌

用比值光谱－导数分光光度法，在ｐＨ５．５缓冲溶液中，利用金属－２－（５－溴－２－吡啶偶氮）－５－二乙氨基酚（５－Ｂｒ－ＰＡＤＡＰ）－ＯＰ三元络合物显色体系，对混合物中铁，铜，锌三组分进行了同时测定。合成试样５次测定回收率在９７．３％－１０４．４％之间。应用于铝合金中铁，铜，锌的测定，各６次测定的ＲＳＤ分别为３．６６％，１．３８％，２．０３％。     

8-羟基喹哪啶固相萃取光度法测定水样中的铁

研究了8-羟基喹哪啶与铁的显色反应，在pH为8．0的氯化氨-氨水缓冲介质中，在十六烷基三甲基溴化铵(CTMAB)存在下，8-羟基喹哪啶与铁反应生成3：1稳定的蓝紫色络合物，该络合物可被Waters Sep-Park-C18固相萃取小柱萃取，用乙醇洗脱后用光度法测定，络合物λmax=600nm。在此波长下其它金属离子的络合物无光吸收，对铁选择性很好，铁含量在0-5mg/L内符合比尔定律，方法用于水样中痕量铁的测定，结果令人满意。     

5,15-二(对-取代苯基)八烷基卟啉及其金属配合物的合成

本文报道了五种5,15-二(对-取代苯基)-2,8,12,18-四乙基-3,7,13,17-四甲基卟啉(Ⅱa—Ⅱe)和五种5,15-二(对-取代苯基)-2,3,7,8,12,13,17,18-八甲基卟啉(Ⅰa—Ⅰe)以及它们的铜、铁、镍金属配合物的合成。这些化合物的结构均经元素分析、UV、~1HNMR和MS鉴定。芳环上不同取代基对卟啉成环反应有一定影响,拉电子基团有利于反应。其顺序如下:NO_2>H>CH_3>OCH_3>N(CH_3)_2。     

铁系元素冠醚配合物的研究——V.三氯化铁与4′-溴苯并-15-冠-5固态配合物的合成和性质

本文报导了三氯化铁(水合物)与4′-溴苯并-15-冠-5(L)固态配合物的合成,对合成的新配合物,进行了元素定量分析及摩尔电导测定,并作了红外光谱、紫外光谱,热重和差热以及X-射线粉末衍射分析的性质表征。从而证明,该配合物中FeCl₃与配体L比为1:1,是溶化剂,含有结晶水的固态配合物。