Komplexe der Alkalimetalltetraphenylborate mit makrocyclischen Kronenethern

Complexes of the Alkali Metal Tetraphenylborates with Macrocyclic Crown Ethers Alkali metal tetraphenylborates, MB(C₆H₅)₄ (M = Li to Cs), react in tetrahydrofuran with macrocyclic crown ethers to give complexes of the general formula MB(C₆H₅)₄(crown)_m(THF)_n. Suitable single crystals for X‐ray structure analysis were grown from a solvent mixture of tetrahydrofuran and n‐hexane. The salt like complexes [Li(12‐crown‐4)(thf)][B(C₆H₅)₄] ( 1 ), [Na(15‐crown‐5)(thf)][B(C₆H₅)₄] ( 2 ), and [Cs(18‐crown‐6)₂][B(C₆H₅)₄] · THF ( 6 ), the mononuclear molecular complexes [KB(C₆H₅)₄(18‐crown‐6)(thf)] ( 3 ), [RbB(C₆H₅)₄(18‐crown‐6)] ( 4 ), and [CsB(C₆H₅)₄(18‐crown‐6)] · THF ( 5 ), and the compound [CsB(C₆H₅)₄(18‐crown‐6)]₂[Cs(18‐crown‐6)₂][B(C₆H₅)₄] ( 7 ), which contains a binuclear molecule ([CsB(C₆H₅)₄(18‐crown‐6)]₂) beside a [Cs(18‐crown‐6)₂]⁺ cation and a [B(C₆H₅)₄]^? anion, are described. All compounds are charactarized by infrared spectra, elemental analysis, NMR‐spectroscopy, and X‐ray single crystal structure analysis.     

熔融萘萃取铁(Ⅱ)-4,7-二苯基-1,10-菲啰啉-四苯硼酸盐三元络合物光度法测定铁

研究了以熔融萘作为萃取剂,以4,7 二苯基 1,10 菲口罗啉作为显色剂,测定天然水中微量铁的分光光度法。在pH4的条件下,铁(Ⅱ)与4,7 二苯基 1,10 菲口罗啉和四苯硼酸盐能够形成红色三元络合物。在熔融萘存在下,此络合物可以迅速萃入熔融萘。将含有络合物的萘冷却、固化、分离,配制成25mL丙酮溶液,对其进行分光光度分析。实验表明,该络合物最大吸收波长为534nm,摩尔吸光系数和桑德尔灵敏度分别为2×104L·mol-1·cm-1和0.0025μg/cm2,铁(Ⅱ)的质量浓度在0～2 0μg/mL的范围内符合比耳定律。大多数常见离子不干扰测定。已应用于天然水中微量铁的测定。     

An Efficient General Synthesis of Squarate Esters

An efficient and general method for the synthesis of alkyl squarates is presented. This involves the reactions of squaric acid with the desired alcohol in the presence of an orthoformate. This was applicable for the synthesis of dimethyl-, diethyl-, diisopropyl, di-n-butyl and di-t-butyl squarates in yields ranging from 77–97%. It is a convenient and safe method that can be accomplished on a multigram scale.     

N-Acyl 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) tetraphenylborate salts as O-acylating agents

Air-stable and crystalline N-acyl DBN tetraphenylborate salts have been shown to be effective O-acylating agents, reacting with both primary and secondary alcohols to give the corresponding esters in good yields. In the case of diols, the N-acyl DBN·BPh₄ salts have been shown to acylate regioselectively the primary alcohol functionality in the presence of a secondary alcohol. The DBN hydrotetraphenylborate side product can be readily removed by filtration, providing the ester products without the need for further purification.     

Determination of electroosmotic flow mobility with a pressure-mediated dual-ion technique for capillary electrophoresis with conductivity detection using organic solvents

A method is described for the indirect determination of the mobility of the electroosmotic flow (EOF), which can be carried out within a few minutes even for very low mobilities. It is independent of the direction of the EOF. It is based on the comparison of the measured mobilities of two oppositely charged reference ions (tetraphenylphosphonium and tetraphenylborate) with given mobilities in different organic solvents (methanol, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, propylene carbonate) at ionic strengths between 5 and 50 mM. The method is based on the sequential movement of the reference ions in a three-step process: first by a laminar flow to a certain position in the separation capillary, followed by electromigration due to application of voltage, and pressurised migration towards the detector. In this way the total mobilities of the reference ions can be determined from their residence times, and the difference to their known actual mobilities gives the mobility of the EOF. The method avoids misinterpretations caused by system- and eigen-peaks, which often bias the results especially when a conductivity detector is used. The method is suitable for all solvents, and is an advantage especially for organic and mixed aqueous–organic background electrolytes with high UV absorbance.     

A novel reaction producing the rhodium(I) complexes with π-coordinated tetraphenylborate anion, (π-PhBPh3). X-ray study of [Rh(PPh3)2(π-PhBPh3)]

Treating the complexes [Rh(TFA)(PPh₃)₂], [Rh(HFA)(PPh₃)₂], and [Rh(TFA)(Cod)] (TFA - trifluoroacetylacetonate, HFA - hexafluoroacetylacetonate, Cod - 1,5 cyclooctadiene) with an excess of NaBPh₄ in acetonitrile yields the rhodium(I) complexes with coordinated [BPh₄]⁻ anion, [Rh(PPh₃)₂(π-PhBPh₃)] · 2MeCN (I) and [Rh(Cod)(π-PhBPh₃)] (II). The reactions present a new example of β-diketonate ligand replacement. The ¹H, ³¹P, and ¹¹B NMR spectra of I and II are discussed. [Rh(PPh₃)₂(π-PhBPh₃)] has been characterized by single crystal X-ray analysis.     

碘解磷定的ICP-AES测定

利用等离子体发射光谱法间接碘解磷。在pH5．0的溶液中，当四苯硼钠过量时可完全沉淀碘解磷定，测定滤液中剩余的四苯硼钠，使可计算得到碘解磷定的含量。该方法简单、快速，回收率在97％－101％之间，相对标准偏差小于2．1％。     

四苯硼钠沉淀／ICP－AES间接测定药物奎宁的研究

本文提出了以四苯钠为沉淀剂，ＩＣＰ－ＡＥＳ间接测定药物成份奎宁的新方法。对影响沉淀反应的条件进行了详细考察和优化，在选择好的实验条件下，本法的检出限为０．０７μｇ／ｍＬ，ＲＳＤ为４％。实验表明，较大量的基体（碱土金属Ｃａ和Ｍｇ）存在对测定结果无明显影响，但可与试剂反应的Ｋ＋、产生正干扰。本法已用于复方奎宁注射液中有效药物成份的测定，分析结果满意。     

原子吸收光谱法间接测定硫酸阿托品

研究了原子吸收光谱法间接测定硫酸阿托品的方法。在pH为5．0的溶液中，当四苯硼钠过量时可完全沉淀硫酸阿托品，在滤液中加入过量的氯化钾沉淀剩余的四苯硼钠，再测定过量的钾可以计算得到硫酸阿托品的含量。方法简单、快速，回收率在97％－101％之间，相对标准偏差为1．1％。     

The Electrochemical Properties of Co(TPP), Tetraphenylborate Modified Glassy Carbon Electrode: Application to Dopamine and Uric Acid Analysis

We report the combination of the charge repelling property of tetraphenyl‐borate (TPB) anion and the electrooxidation catalytic effect of cobalt(II) tetrakisphenylporphyrin (CoTPP) embedded in a sol gel ceramic film to develop a modified glassy carbon electrode (CoTPP‐TPB‐SGGCE) for the simultaneous determination of dopamine (DA) and uric acid (UA). The optimized CoTPP‐TPB‐SGGCE shows excellent sensitivity and selectivity for the DA and UA analysis. As high as 2000 fold acceptable tolerance of ascorbic acid (AA) for the determination of trace DA and UA is reached. In the presence of 0.10 mM AA, the linear concentration range for DA is from 6.0×10^?8 to 2.5×10^?5 M, and the detection limit is 2.0×10^?8 M. For UA, the linear concentration range is from 1.0×10^?7 to 3.5×10^?5 M, and the detection limit is 7.0×10^?8 M. Our study has also demonstrated that the novel CoTPP‐TPB‐SGGCE shows high stability and reliability. For 6.00 μM DA and UA, a total of 12 measurements were taken in one week, and the relative standard deviation is 2.05% and 2.68% respectively. No obvious shift of peak current and peak potential is observed over a three‐month lifetime test. The response of the sensor is very quick and response time is approximately 1 s. Satisfactory results are also achieved when the CoTPP‐TPB‐SGGCEs being used to detect the DA and UA in human urine samples.